WO1998052993A1

WO1998052993A1 - Boron-containing polymer material having protective functional structure and its preparation

Info

Publication number: WO1998052993A1
Application number: PCT/CN1998/000072
Authority: WO
Inventors: Shenggang Zhou
Original assignee: Shenzhen House Safety Investment Co., Ltd.
Priority date: 1997-05-19
Filing date: 1998-05-14
Publication date: 1998-11-26
Also published as: AU7330198A

Abstract

The present invention provides a boron-containing polymer material having self-adaptive protective functional structure and its preparation, said material has boryl or boroxy center constituting main structure together with organic active group and has 50-80 % structural water and combination water based on the total weight of said material; wherein, the organic active group described herein selects from the groups consisting of hydroxy group, aldehyde group, ketone group, carboxylic group; the combination water described herein refers to natural absorbed free water when said material is produced and various morphological water molecule in reactive filler; the structural water described herein refers to all of H and O elements forming said material functional structure, its level ratio is approximately 2:1. The material of the present invention can be used in high temperature heat insulation, high temperature antioxidation, fire retarding and flame resistance, radiation absorption nuclear radiation shielding and high-energy beam shock.

Description

Boron polymer material with protective function structure and preparation method thereof

The invention relates to a boron polymer material with an adaptive protective function structure and a preparation method thereof, and in particular, to a protective function with high-temperature insulation, high-temperature oxidation resistance, fire retardancy, radiation absorption, nuclear radiation shielding, and high-energy beam impact resistance. Structural materials and methods of making them. The so-called "adaptiveness" refers to a continuous physical and chemical comprehensive reaction with a protective effect caused by environmental conditions, especially temperature changes, and the protective response has a dynamic corresponding property; the so-called "protective functional structure" refers to the elements of the structure on the one hand The proportion and element structure are reasonable. On the other hand, it is required that the structure does not collapse instantaneously under the action of high temperature or high temperature kinetic energy, but has a directional transition from one adaptive structure to another adaptive structure. Part of the transformation is reversible.

Background technique

For traditional high temperature heat insulation and fire retardant materials, the technical solution advocated by classic theory mainly uses inorganic hollow porous low density heat insulation refractory materials, high melting point refractory materials and low thermal conductivity materials; radiation absorption and nuclear radiation shielding mostly use other natural materials. Inorganic materials and heavy metals and their oxide materials. The main defects of traditional technology are summarized in five aspects: 1. Material performance is single and does not have good technical characteristics in two or more fields; 2. There is a certain degree of environmental pollution in production or use; 3. Effective work Most of the temperature is about 1000 'C, and the applicable temperature is up to about 2000' C. 4. The heat insulation is not adiabatic--Only the structure of the thermos flask is within a very narrow range of temperature difference of 300'C-600'C. It has adiabatic effect; 5. The commercial cost of the price / performance ratio is high, and it cannot meet the growing social needs.

In the past ten years, new protective materials with enhanced or extended performance have appeared. Among them, the main composition characteristics of materials with better performance are distributed in three aspects: 1. Inorganic strong covalent bonding materials, such as carbon fiber, silicon carbide fiber and boron carbide materials; 2. Silicon boron, carbosilicon boron, and borane Polymer organic materials and their composite materials that are the dominant trend; 3. Organic composite materials with phosphides, borides, and halogenated flame retardants. These materials improve the performance of certain applications or have a certain comprehensive technical performance, but also bring new deficiencies or there are still unsatisfactory:

1. Increased environmental problems, including the leakage of poisons in the production process, the release of harmful gases from high temperature and heat release, or environmental pollution after disposal;

2. The cost has risen sharply, which is not conducive to popularization, especially unsuitable for large-scale protection market demand in cities;

3. The applicable temperature of flame retardant in the air is below 800 'C-1000' C, which is not much different from traditional technology; 4, can not meet the comprehensive needs of today's high-precision, sophisticated areas;

5. In terms of comprehensive protection performance, there is no qualitative or major breakthrough in traditional technology.

In short, the existing technology is influenced by the tradition of the classical theory, emphasizing that the constant (performance) should be changed (integrated protection guarantee), and the result restricts the overall development of protective materials.

From the 1980s to the present, the analysis of the shortcomings of the existing patent literature in terms of comprehensive protection technology solutions and their material properties is as follows.

I. The elemental composition of the material is unreasonable

1.1. Harmful elements containing halogen, sulfur, phosphorus, and heavy metals-High-temperature thermal decomposition is likely to produce toxic asphyxiating gases or substances that are likely to pollute the environment. Patent documents include US85-4504611, US85-4506036, US5179048, US4910173, US93-5272237, JP91-289338, and other halogen-containing elements; JP91-305218, tebupine 7-278267, and other phosphorus-containing elements; JP87-130782 contains lead.

1.2. The composition of organic materials H, 0, and B is unreasonable--Almost or most of them are combinations of excess hydrogen or oxygen, including the presence of elemental boron. A large amount of heat is generated at high temperatures, which is not conducive to high temperature protection. These patent documents include: US85-4504611, US93-5272237, JP87-38874, JP87-107226, JP89-268706, JP94-121540, JP94-125564, JP 7-41611, JP 7-118498, etc. High; US89-338218 oxygen content is too high; JP83-175292 contains elemental boron.

Second, the molecular structure of the material is unreasonable

2.1. The core element boron of the flame retardant should not directly form a molecular structure with elements other than C, 0, N, otherwise it is not conducive to high temperature oxidation resistance or to form a stable protective structure under high temperature conditions. Such as patent document: US5179048.

2.2. The overall molecular structure is unreasonable

US85-450461 1 uses non-boron-based molecular structures such as cyclooctyl hexachlorocyclopentane and polyamines, which is not conducive to the formation of anti-oxidation reactions at high temperatures, and its high chlorine content also easily releases harmful gases; 'US93- 5272237 adopts the molecular structure of acetylene carboboron-siloxamidine. Since the boron group is on a branched chain, there is no better high temperature application effect.

2.3. Functional structure without protection

The specific molecular structure of each of the above documents did not take into account the design of the protective function, nor did it design the molecular structure required to meet the comprehensive application requirements to determine the amount of elements. Third, the lack of technical solutions

3.1. Documents such as W095-11272, US85-4504611, JP-A-7-28267, etc. are all combined technologies of organic substances and flame retardants, which do not constitute new material materials, so it is difficult to have greater advantages than traditional technical solutions.

3.2. US5223461 inorganic silicon boron carbon porcelain fiber and other high temperature resistant materials have complicated technology and high cost, and are not suitable for mass production and commercial development. In addition, US85-4506036, US88-261104, and US4910173 are not conducive to demand in large markets. Price / feature ratio.

3.3. W095-11272 contains aldehyde toxicants and the above-mentioned literature (has been pointed out) synthetic materials containing halogen, phosphorus and heavy metal elements are easy to harm the environment and production personnel during the production process.

4. Thermal decomposition pollution in protective applications

Although Ping 7-27826 does not contain halogen, it contains harmful flame retardants such as phosphoric acid in its synthesis, and can generate toxic phosphoric acid vapor and other harmful gases in high heat, which pollutes the environment.

V. Other issues

5.1. US75-3891621 is a glucopyranoside-containing boropolymer and its derivative, in which the alkylboronyl group is in an important position in the structure between sugar alcohols. However, due to improper selection of the raw material reactants, that is, the reactants contribute to the biological elements Η: 0 ≥ 4: 1, the hydrogen element easily burns and generates heat at high temperatures, and the production preparation method is not optimized, that is, the orientation of the structured water is not increased in the reaction preparation method. Process reaction, so there are many deficiencies in the technical system-in addition to the previous analysis, there is also a very low structural water content (about 36%), and no functional structure is formed. Therefore, high temperature insulation, resistance to high energy beam impact and radiation Poor performance such as shielding.

5.2. JP87-38874 uses a water-soluble polycondensation preparation method. The main raw materials are also inorganic borides, such as boric acid. The shortcomings are mainly reflected in the choice of reactants to be fluorinated hydrocarbon groups or chloride compounds. The former generates a large amount of heat at high temperatures, which is not conducive to it. Fire and flame retardant, the latter chloride is liable to produce harmful gases or pollution components in the fire. The disadvantage of the method is also that the directional process reaction of structured water is not added in the preparation method. No better protection. This method does not exhaust its advantages, mainly because the aqueous solution is only used as a solvent, and it does not strengthen the formation of structured water and bound water, so it cannot be a good functional protective material. Secondly, the boro-silicon base is integrated, which is not conducive to high temperature resistance to carbon oxidation. In short, the existing technology is very serious about the protection system. The key is the limitation of protection theory and concept.

In short, in today's high-precision protection field, structural engineering materials with protective functions and comprehensive protection application solutions such as sustainable development of the environment, it is difficult to find the answer to the problem in the existing technology. In our high-tech era, we need a protective functional material with the following excellent technical properties: 1. Meet the high temperature protection requirements above 1000 'C-3500' C in a specific time or 350 'C-2000 under specific conditions. Long-term application requirements between C;

2. In contrast to the prior art, the thermal decomposition of functional materials and adaptive reaction changes are used to achieve the goal of higher thermal conductivity and lower thermal conductivity. For example, the thermal conductivity between 700-3600 ° C is smaller than traditional thermal insulation materials 2- 4 orders of magnitude;

3. Realize the comprehensive ability of high-temperature anti-oxidation, control of thermal neutron absorption and nuclear shielding, so as to control and block the thermonuclear reaction of the general fire from the thermal nuclear power plant accident exceeding the 1500 'C limit. ;

4. Urban and forest fire protection not only needs to give full play to the protective performance of functional materials, but also needs to adaptively expand the supply of fire disaster mitigation resources (such as water resources) with the help of protected items (such as carbohydrate wood);

5. It is required to achieve the goal of greening throughout the process, including at the scene of disasters such as fires, the material itself does not produce harmful gases and harmful substances, and it must also suppress the generation of harmful gases in contact with the articles;

6. It is necessary to give full play to the potential of multi-function and achieve the goal of more effectively resisting the impact of high-energy beams than existing high-melting substances.

At the same time, the present invention also provides a protective material having the following characteristics:

1. High temperature insulation, its dynamic thermal conductivity is only 1%-10% of traditional low value materials;

2. High temperature anti-oxidation, make the carbon and organic carbonized substances at 800. C-not easy to oxidize at high temperature of 3000 ° C-to help block fire heat source;

3. Thermonuclear firefighting, which can absorb thermal neutrons while also losing nuclear energy-control and block the ongoing of thermonuclear accidents;

4. High-energy impact resistance, the impact resistance of high-energy beams such as lasers exceeds any existing materials;

5. The commercial cost is suitable, and it can be mass-produced and easy to be widely used.

In order to achieve the purpose of developing protective functional materials, the present invention forms an organic boron polymer with a protective functional structure by using inorganic boride and organic matter or sugars, so that it can be used under adaptive dynamic (thermal reaction / thermal decomposition) conditions The above-mentioned excellent technical performance is produced, so that organic functional materials are used to achieve high-precision and cost-effective comprehensive protection purposes.

Therefore, the object of the present invention is to overcome the shortcomings in the prior art, and to provide a material with a protective function structure having adaptive dynamic characteristics and a preparation method thereof. Summary of invention

The object of the present invention is achieved by providing a boron polymer material with a protective function structure. The material has a main structure with a boron group or a boroxy group as the center and an organic active group, and has Structured and bound water with a total weight of 50-80%;

The organic active group is selected from the group consisting of a hydroxyl group, an aldehyde group, a ketone group, and a carboxyl group;

The bound water refers to free water naturally adsorbed when the material is generated and water molecules in various forms in the reaction filling;

The structured water refers to all H and 0 elements constituting the functional structure of the material, and the content ratio is 1.6: 1-2.5: 1.

A material provided by the present invention is that the main structure composed of a boron group or a boronoxy group and an organic active group contains one or more of the following structural units:

-^ c-B-Sc}. R'-Sc-B-Sc-R. M-Sc-B-Sc-R (M) R-B-Sc-R (M)

M (OH / H)

(al) (a2) (a3) (a4)

+ Sc-0-B-0-Sc + R, -Sc-0-B-0-Sc-R ₂ (M) M-Sc-OBO-Sc-R (M) (^) Η (Ο) OH (O ) OH (O)

(a5) (a6) (a7)

MOBO-Sc-R (M) MB- (0) -Sc-R (M) (M'B) _n Sc +

I

OH (O) OH (0 / M) n = l-120

(a8) (a9) (alO) where:

Sc is a glycosyl;

R, R, and R ₂ are an oxygen-containing organic group or an alkane group;

M is a base or other inorganic root.

The main structure of the above materials may further contain one or more of auxiliaries, modifiers, and fillers to form a marginal functional structure having the following general formula:

MC (l) /., ..... / (10H C MC '[(1) / …… / (10)] -MC MC (1) / …… / (10)] -MC

(al l) (al2) (al3) where

MC is a stabilizing group of a modifier or stabilizer; The auxiliary agent is selected from one or two selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, silica, and non-toxic organic acids;

The modifier is selected from the group consisting of alkaline earth metal hydroxides, fourth-cycle metal oxides, fourth-cycle metal hydroxides, antimony and tin compounds, ammonia or alkali metal silicates, ammonia or alkali metal carbonates, One or two of the group consisting of ammonia or alkali metal organic acid salt, gum arabic, and active silica;

The filler is selected from alumina, aluminum hydroxide, aluminum compounds, titanium oxide, titanium hydroxide, magnesium double oxide, calcium hydroxide, poorly soluble silicates and carbonates, silicon powder, boron powder, and carbides. , Insoluble carbohydrates, natural adhesives, one or more of the group consisting of halogen / sulfur / phosphorus-free synthetic resins and their adhesives.

Another material provided by the present invention is that the main structure composed of a boron group or a boronoxy group and an organic active group contains one or more of the following structural units:

_{_{-rO R BR 2 -O 2 - ^}} - + D 1 -R 1 -BR 2 -D 2 + + D r R r BR 2 -D 2 - 0- M OH

(bl) (b2) (b3)

(H) M-0-B-R-D,-(R ^ D.-O-B-R ^ -D,--(M) H-B-R-D- OH (H) M M (0)) (b4) (b5) (b6)

-(R,) D, -0-B- D ₂ (R ₂ ) +

OH (0 / H / M)

(b7)

R, R, and R ₂ are the same or different oxygen-containing organic groups;

M is a base or an inorganic root.

: VlC + (l) / …… / (17) + MC MC-[(1) / …… / (17)] -MC MC-f (l) / …… / (17)] -MC

(b8) (b9) (blO) where

MC is a stabilizing group of a modifier or stabilizer;

The auxiliary agent is selected from the group consisting of metal organic catalyst, silicon oxide, boron oxide, alkali metal hydroxide, and alkali. One or more of the group consisting of earth metal oxide shrinkage agent, alkaline earth metal silicide powder, carbon powder, semiconductor elementary ultrafine particles, resin ion adsorbent, amphoteric metal oxide, amino acid and other pH buffer adjusters; The modifier is selected from the group consisting of metal oxides, metal hydroxides, carbonates, silicas, silicates, volatile non-toxic or slightly toxic alcohols and ester solvents, active groups containing metal elements, elemental carbon, stable metals One or more of the group consisting of powder, natural organic matter and its binder, synthetic resin and its binder, and ultraviolet absorber;

The filler is any inorganic or organic substance which does not directly react with boron-based or ammonia solution, alcohols, alkali metal alcoholates, aliphatic carboxylic acids and derivatives thereof, and alcohol amines.

The invention further provides a method for preparing a boron polymer material with an adaptive protective function structure, which is a reaction of a substance having a hydroxyl group, an aldehyde group or a ketone group with an inorganic boride to produce a compound having a boron group or a boronoxy group as The center and the organic active group constitute a main structure, and have structured water and bound water which account for 50-80% of the total weight of the material;

The structured water refers to all H and 0 elements in the material, and the content ratio is close to 1.6: 1-2.5: 1;

The inorganic boride is selected from one or more of metal boride, boron oxide, boric acid and its salts, metaborate, tetra / pentaborate, and perborate.

The present invention also provides the above-mentioned boron polymer material with a protective function structure in the preparation of a) 200. C-3500 'C high temperature insulation; b) 300 ° C-4500 ° C high temperature oxidation resistance; c) 350' C-5000 'C fire and flame retardant; d) 2500 ° C-10000' C above high energy beam impact resistance; and e) Thermonuclear control below 2000 ° C-3000 'C and its application in fire protection and shielding products; and, in preparation a) 260. C-2700 'C high temperature insulation; b) 350' C-3500 'C high temperature oxidation resistance; c) 400' C-4500 fire and flame retardant; d) 1800. C-5000 'C Application in high energy beam impact resistant products. The product may be an engineering structural material or a decorative material.

The present invention is described in detail below.

Detailed description of the invention

I.

The substance having a hydroxyl group, an aldehyde group or a keto group is selected from the group consisting of monosaccharides, disaccharides, trisaccharides, polysaccharides, sugar acids and their metal salts, ammonium sugar acids, water-soluble cellulose and their salts, and sugars ( Class) composed of organic cellulose When one or more saccharides in the group are in water or an aqueous solution containing an alcohol and an alcohol derivative, an inorganic boride containing no halogen, sulfur, phosphorus, and arsenic, and the saccharides and derivatives are derived. React with each other to form a sugar-boron copolymer having one or more of the aforementioned functional structures (al)-(alO).

-^ Sc-B-Sc ^, -Sc-B-Sc-R ₂ M-Sc-B-Sc-R (M) RB-Sc-R (M)

M (0 shall)

(al) (a2) (a3) (a4)

■ Sc-OBO-Sc-f R, -Sc-0-B-0-Sc-R ₂ (M) M-Sc-OBO-Sc-R (M) I 1

0H (0) 0H (0) 0H (0)

(a5) (a6) (a7)

M-O-B-O-Sc-R (M) M-B- (0) -Sc-R (M) (M-B) `` Sc-]-I

0H (0) OH (0 / M) n = l-120 (a8) (a9) (alO) The specific requirements for implementing the technical solution of the present invention are as follows:

A. Control and selection of raw materials and technical requirements

A1. The control principle of raw materials. All raw materials participating in the reaction or non-reaction (filler) must not contain harmful substances and harmful elements that exceed environmental standards, nor do they contain halogen, sulfur, phosphorus, and arsenic that are potentially harmful at high temperatures. And heavy metal elements.

A2. Optimal protection performance

A2-1. The ratio of the content of H to 0 in the total product (organic matter) should be close to 2: 1, and generally controlled within the range of H: 0 = 1.6: 1-2.5: 1;

A2-2. The functional structure is to ensure as much structural water content as possible, so carbohydrates are selected as the main reactants-water-soluble substances are one of the reactants that make up the functional structure, and water-insoluble substances are used as fillers. One;

A2-3. In the functional structure, it is necessary to ensure that a proper amount of boron group or boryloxy group exists, so the inorganic boride is selected (acid / base / salt) water-soluble boride;

A2-4. There must be as much stable water as possible in the product, so water or alcohol-containing aqueous solution is the medium and the reactant in the reaction;

A2-5. In order to achieve comprehensive protection requirements, it must be ensured that the structured water and bound water in the total product reach 30-75%.

A3. Water or an aqueous solution containing 0.1-50% alcohol and derivatives is an intermediate reactant of the present invention, wherein the alcohol One or more selected from the group consisting of ethanol, ethylene glycol, glycerol, pentaerythritol, sorbitol and the like; non-toxic polyols are preferred (preferable range should be less than the aforementioned range).

A4. The inorganic boride is selected from one or more of the group consisting of metal boride, boron oxide, boric acid (salt), metaborate, tetra / pentaborate, and perborate; preferably, boride Aluminium (zinc / sodium / magnesium), boron oxide, boric acid, sodium (potassium) borate, sodium metaborate (potassium), (aqueous) sodium tetraborate (potassium), ammonium pentaborate, sodium perborate Or more.

A5. Carbohydrates and their derivatives are selected from the group consisting of monosaccharides, disaccharides, trisaccharides, polysaccharides, sugar acids and their metal salts, sugar acid ammonium salts, water-soluble cellulose and their salts, and sugar (class) organic derivatives. One or two of the group; preferably a group consisting of monosaccharides, disaccharides, trisaccharides, hydrolysable polysaccharides such as starch, gluconic acid and its sodium (zinc) salts, hydroxycellulose and CMC, sugar esters One or two.

A6. The auxiliary is selected from one or two of the group consisting of sodium hydroxide (potassium hydroxide), ammonia, silica, and non-toxic organic acids; preferably, sodium hydroxide, ammonia, sodium silicate, lactic acid, and synthetic fatty acids , Oxalic acid, acetic acid.

A7. The modifier is selected from the group consisting of alkaline earth metal hydroxides, fourth-cycle metal (hydrogen) oxides, antimony and tin compounds, ammonia or alkali metal silicic acid (carbonic acid / organic acid) salts, gum arabic, and active silica. One or two of the group; preferably made of calcium hydroxide (magnesium hydroxide), (hydrogen) titanium oxide (zinc / copper / manganese), ammonium antimonate (sodium / bell), sodium stannate, sodium silicate, carbonic acid One or two of the group consisting of (hydro) ammonium, weak base salts of organic acids, gum arabic, fumed silica, and white carbon black.

A8. The filler is selected from (hydro) alumina, aluminum compounds, (hydro) titanium oxide, magnesium (calcium) hydroxide, poorly soluble silicates and carbonates, silicon powder, boron powder, carbides, insoluble carbohydrates Natural adhesives, one or more of the group consisting of halogen / sulfur / phosphorus-free synthetic resins and their adhesives; preferably composed of (hydrogen) aluminum oxide, aluminum powder, aluminum silicate, (hydrogen) oxidation Titanium, magnesium hydroxide, quartz sand, calcium carbonate, magnesium trisilicate, silicon powder, boron powder, activated carbon powder, carbon fiber, sawdust, natural rubber, epoxy resin and its curing agent, unsaturated polyester, silicone One or more of a group consisting of a polymer and an acrylic resin.

B. Reaction Synthesis Methods

It has been found that in the aqueous solution, various borate groups easily undergo polycondensation and esterification with the hydroxyl groups on the sugar to form borooxy sugar boron polymer groups; or in the role of alkali metal ions In the following, boron radicals easily undergo a substitution reaction and a coupling reaction with a hydroxyl group on a sugar to form a boron-based sugar-boron polymer group. Experiments have shown that both types of groups are prone to crystal growth in multiple states. This shows that a boron (oxygen) Can be combined with a single polyhydroxy sugar molecule, or can be copolymerized with two or three sugar molecules; in contrast, a single sugar can be combined with a single boron (oxy) group, or with two or three to six boron ( Oxygen) group. In the present invention, in order to select a better protection effect, the latter copolymerization group is mainly selected as the main functional structure in terms of the amount of raw materials and the reaction method.

B1. Mix the (aluminum / zinc / sodium / magnesium) metal boride with the sugars in water or an alcohol-containing aqueous solution; if a monosaccharide or disaccharide is selected, then at normal temperature or 50 ' Co-solvent reaction under C-80 'C conditions; if trisaccharides or polysaccharides (such as starch) are present, it is necessary to co-solve in a bath heat condition of 70' C-150 "C. The boron-based sugar boron polymer formed during the reaction The typical functional structure of the group is:

(al) (a2) (a3) (a4) wherein Sc is a sugar, R, R is an oxygen-containing organic group or an alkane group on a sugar group, and M is a base or an inorganic root. To promote this reaction, an appropriate amount of organic acid or inorganic basic compound is added to the intermediate reaction solution.

B2, the (partial / over / four / five) borate and the saccharides are mixed in water or an alcohol-containing aqueous solution, and reacted at room temperature or in a 50 'C-100' C bath by thermal co-solubilization. Reaction The typical functional structural formula of the borooxy sugar boron polymer group produced in

+ Sc-0-B-0-Sc-f R, -Sc-0-B-0-Sc-R ₂ (M) M-Sc-OBO-Sc-R (M) I

OH (O) OH (O) OH (O)

(a5) (a6) (a7)

MOBO-Sc-R (M) MB- (0) -Sc-R (M) (M'B) _n Sc +

I

OH (O) OH (0 / M) n = l-120

(a9) (alO)

Each symbol in the formula is the same as Bl. To promote this reaction, the auxiliaries can be added to the intermediate reaction solution.

B3. In the above-mentioned mixed solution, the (al)-(alO) group contains sugar aldehyde group and ketone group, so the functional structure at this time is still unstable. Further technical treatment; or stand for several days at room temperature, naturally grow (micro) crystals to form the basic product of protective function structure; or add modifiers or fillers (should use the waste heat), in a multi-component mixed solution Formation of complex synthetic reactions-(addition reactions on aldehydes and ketone groups), esterification reactions, cross-linking reactions, etc. These reactions not only stabilize functional groups, but also form marginal functional structures MC (al) / …… / (alO)-] MC MC '[(al) / …… / (alO)] -MC MCf (al) / …… / (alO)] -MC

Derivatives of (al l) (al2) (al3), where MC-/ MC is a stabilizing group of a modifier or filler, including metal (oxide) powder that absorbs radiation. (Al l)-(al3) Form a product with a protective function structure that has the physical and chemical characteristics of a family or department and the same heterogeneous appearance effect, (al l) is a metastable structure; (al2) is a free structure; (al3) is Random structure.

C technology implementation plan,

If the polysaccharide is not easily soluble in water, it is first hydrolyzed (the acid or alkali auxiliary agent can be used), and then the following reaction is performed.

C1. According to the weight of the application: 10-200 parts from A4 and 1-100 parts from A5 are mixed in 30-230 parts of A3 intermediary reaction solution, which can be added with A6 auxiliary agent 0-50 parts. The base product is then homogenized at 50 'C-150' C.

C2. Add 0 to 100 parts of A7 agent or 0 to 300 parts of A8 agent according to the weight ratio in the waste heat of the basic product to form a derivative product.

C3. In order to improve the specific gravity and stability of structured water and bound water in the functional structure, the C1-C2 technical solution can be measured in the following optimized ranges:

60-200 parts A3, 30-120 parts A4, 5-60 parts A5, 0-30 parts A6 homogeneous mixed bath heat → 1-60 parts A7 or 1-230 parts A8,

In summary, for the preparation of a class of sugar boron polymers with a protective function structure, in order to increase the proportion of the bound water and structure water H, 0, OH groups in the functional structure, the water or alcohol The water of alcohol and alcohol derivatives is both a reaction mediator and a reactant. Among them, the main reaction methods include two kinds of hydrolysis reaction, displacement reaction / ion exchange reaction, esterification reaction, coupling reaction, polycondensation reaction and cross-linking reaction. Multiple coexisting methods. In the further formation of derivatives, arbitrary synthesis and mixing methods that do not affect the (al)-(al0) functional structure skeleton are used.

In a specific preparation method, a) if the saccharides and derivatives are not directly dissolved in water or an alcohol-containing aqueous solution, then use a bath heat condition of 50'C-150 ° C to hydrolyze or dissolve them in a uniform state; 1>) and the bath thermal hydrolysis reaction of> 100 ° C adopts the corresponding pressure-sealed reaction control technology; c) the solution of sugars and their derivatives in a hydrolyzed or uniformly distributed state with the inorganic at normal pressure and temperature The boride is subjected to a series of copolymerization reactions; or d) the copolymerization reaction is performed under the above-mentioned waste heat conditions at normal pressure. Can be added during the above a)-d) reaction Alternatively, no alkaline or acidic additives are added; and during or after the above a) to d) reaction, modifiers and fillers may or may not be added.

In a specific embodiment, the intermediary reactant is selected from water or an aqueous solution containing 0.1 to 50% of an alcohol-based alcohol derivative in an amount of 30 to 230 parts by weight; 10 to 200 parts by weight of boride ¾1; 1 to 100 parts by weight of sugar And its derivatives; 0-50 parts by weight of auxiliaries; 0-100 parts by weight of modifiers; 0-300 parts by weight of fillers.

In another specific embodiment, a) the intermediate reactant is selected from 30 to 180 parts by weight of water or 50 to 230 parts by weight of an aqueous solution containing 1 to 35% of a polyol and a derivative thereof; b) 50 to 150 parts by weight Part of boride, said boride is selected from alkali-soluble or acid-soluble non-heavy metal boride, boron oxide, boric acid, sodium (potassium) borate, sodium metaborate (potassium), (aqueous) sodium tetraborate (potassium), five One or two of ammonium borate and sodium perborate; c) 3-80 parts by weight of sugars and their derivatives selected from monosaccharides, disaccharides, trisaccharides, hydrolysable polysaccharides, gluconic acid and metal salts thereof, One or two of ammonium sugar acid, hydroxycellulose and its salt, sugar ester; d) 0-35 parts by weight of auxiliary agent, selected from sodium hydroxide, ammonia, silica, sodium silicate, H : 0 * 2: 1 of one of organic acids; e) within the above range according to actual needs, take the amount of blending → bath heat → co-solvent initial polymerization, or cool to room temperature for 1-20 hours to form a basic product or use Waste heat addition f) 0-70 parts by weight of modifier, selected from calcium hydroxide (magnesium hydroxide), (hydrogen ) Titanium oxide (zinc / copper / manganese), ammonium antimonide, sodium antimony (potassium), sodium stannate, sodium silicate, ammonium bicarbonate, acacia gum, weak base salt of organic acid, active silica One or two of them; g) 0-270 parts by weight of filler, selected from (hydro) alumina, (hydro) titanium oxide, aluminum powder, aluminum silicate, magnesium hydroxide, quartz sand, calcium carbonate, tri-silicon Acid lens, silicon powder, boron nitride, boron powder, activated carbon powder, carbon fiber, sawdust, natural rubber, epoxy resin and its curing agent, unsaturated polyester, silicone polymer, acrylic resin and polyamide One or two or three.

In yet another embodiment, the intermediary reactant described in a) is selected from 50 to 120 parts by weight of water or 60 to 200 parts by weight of a non-toxic or slightly toxic alcohol aqueous solution containing 2 to 30%, wherein the alcohol may be ethanol, ethyl Glycols, glycerol, pentaerythritol, sorbitol, etc .; b) 30-120 parts by weight of boride selected from aluminum boride (zinc / sodium / magnesium), boron oxide, boric acid, sodium borate, sodium tetraborate pentahydrate, borax, One or two of ammonium pentaborate and sodium perborate; c) 5-60 parts by weight of sugars and derivatives thereof, selected from disaccharides, trisaccharides, starch, sodium gluconate (zinc), CMC, hydroxymethyl One or two of (ethyl / propyl) -based cellulose and sugar esters; d) 0-30 parts by weight of auxiliary agent, selected from sodium hydroxide, 20-30% ammonia water, silica, sodium silicate powder , Acetic acid, oxalic acid, lactic acid, synthetic fatty acids; e) within the above range according to the actual needs of the amount to be mixed-70 'C-100' C bath Heat / Soaking → Co-solvent primary polymerization, or cooling to room temperature to form a basic product, or use residual heat to add f) 0-60 parts by weight of a modifier, selected from magnesium hydroxide, titanium oxide (zinc), sodium antimony, One or two of sodium stannate, gum arabic, linoleic acid, butenoic acid, fumed silica, and white carbon black; g) 0-230 parts by weight of filler, all mixed to form a product with a protective function structure .

The sugar-boron polymer protective functional material of the present invention has the following superior properties and good effects over the existing static protective materials:

1.High temperature insulation performance ''

The structural change of organic thermal decomposition of (al)-(al 3) formula when high temperature such as 200'C-1000'C or more

> oo ⁰ C

+ Sc- (0) -B- (0) -Sc + (representative formula) → + R- (0) -B- (0) -R + + nH ₂ 0 ~~>

-B-0-C / -BC-/-BN-/-B-MC- + mH ₂ 0 (al4)

MC 'is a high-temperature residue of MC, n + m water loses a lot of heat, and at the same time, it forms a microporous high temperature resistant (2000 -C-3000' C) protective structure. This microporous has good vacuum insulation performance. -The higher the temperature, the better this performance. The combined contribution of both contributes to the good performance of high-temperature insulation. Experiments show that between 800 'C-1500' C, its thermal conductivity is 2 to 3 orders of magnitude lower than the prior art; 1500 'C-3500' C is 3 to 4 orders of magnitude lower.

2. High temperature oxidation resistance

It is mainly the catalytic contribution of boron / boryl groups. Experiments show that 3000 'C-4500 in air still exists. Good application range is 700 'C-3500' C, effective range is about 300. C-4500 'C.

3. Thermonuclear fire performance

The thermal decomposition and heat dissipation of the material of the present invention can be directly performed below 2000 ° C-3000 'C. When a major accident occurs in a thermonuclear power plant, the high water-containing material of the present invention can dissipate a large amount of heat, and can produce it in> 800 1; (al4) The stable structure of the inorganic boron polymer in the formula. Both the H, OH, and M components before thermal decomposition and the inorganic polymer components after thermal decomposition can absorb a large number of thermal neutrons and block the thermonuclear reaction. This double-effect contribution is better than specialty cement, and it is also superior to expensive carbon boron fibers.

4. High-energy beam impact resistance

The material of the invention contains relatively high combined water and structured water, so when it encounters high-energy beam impacts above 2500 'C-10000' C, water vapor will form hundreds to tens of thousands of dynamic atmospheric pressure-shock waves to block High energy beam strike for a long time. Such blocking performance is difficult to compare with any protective material in the prior art.

5. Fire and flame retardant properties

As described in 1-4, the adaptability of the protective material of the present invention can be applied to a wide range of wide-ranging protection fields. Therefore, it is superior to the existing protective flame retardant technology. In reality, many carbohydrates (such as wood and fiberboard) are combustion-supporting materials at the scene of a fire. The existing technology only solves the problem of flame retardancy, and the material of the present invention surpasses the flame retardancy of existing materials in a continuous fire. Performance: On the one hand, dig 56% of "fire-fighting water" (about 56% of carbohydrate-containing structured water) with the help of a high-temperature environment; on the other hand, make the carbonized part not only difficult to burn, but also block its harmful gas generation. The fireproof and flame retardant materials of the invention can be used in the temperature range of 350'C-5000'C.

In short, based on the concept of system protection, the present invention solves the problem of the poor comprehensive effect of static technology in the prior art, which only highlights one characteristic but loses other characteristics.

II.

When the substance having a hydroxyl group, an aldehyde group or a ketone group is selected from the group consisting of oils and fats, aliphatic compounds and their derivatives, organic polymers in natural plants and animals, such as vegetable fats, gums, animal oils and their salts, and synthetic resins In the case of one or more organic substances in the group consisting of oxygen-containing synthetic resin, the inorganic boride is in the presence of the intermediate reactant hydroxyorganic substance and its derivative or aliphatic hydroxy acid and its derivative or alcohol amine or chlorine It reacts with organic compounds that do not contain halogen, sulfur, phosphorus, and arsenic to form a copolymer with a boron group or a boronoxy group as the functional structure. The copolymer is one of the following units (bl)-(b7) or A variety of organic copolymers.

-D, -R, -D, +

(bl) (b2) (b3)

(H) M-0-BR-D + + (R ₁ ) D ₁ -0-BR, -D, + (M) HBR-D +

I "" t

OH (H) M M (OH / H)

(b4) (b5) (b6)

+ (R ') D'-0 †-D ₂ (R ₂ ) +

OH (0 H / M)

(b7)

The specific requirements for realizing the above technical solution of the invention are as follows:

A. Raw material selection Al. Selection principle. Any organic or inorganic chemical products and natural substances that do not cause harm or potential harm to the environment can be considered as the primary or secondary raw materials for the reaction.

A2. In order to realize the protective function of thermal reaction / thermal decomposition, the present invention uses a boron group or a borooxy group as the core and an organic group as a bond to form a protective function structure of a macromolecule. Therefore, organic matter and boride are the main materials of choice.

A3. Raw material selection scheme, each reactant is mainly composed of C, H, 0, Si, B, Na, N and other elements, and other alkali metals, alkaline earth metals, fourth-cycle transition metal elements and aluminum, germanium, antimony, etc. auxiliary. The reactants of the present invention are classified as follows:

A3-1 Inorganic boride includes metal boride, boron oxide, boric acid and its salts, sodium perborate (potassium) and other perborate, metaborate, ice-free tetra / pentaborate, sodium borohydride (Potassium);

A3-2 Organic matter includes oils and fats, alicyclic compounds and their derivatives, organic polymers and salts of natural plants and animals, and (oxygen) synthetic resins;

A3-3 intermediary reactants include ammonia solution, alcohols, alkali metal alcoholates, aliphatic carboxylic acids and their ester derivatives, non-toxic or slightly less toxic alcohol amines;

A3-4 Auxiliaries include: metal organic catalyst / or silicon oxide, boron oxide, alkali metal hydroxide, alkaline earth metal oxide shrinking agent / or silicide powder, carbon powder, semiconductor element ultrafine particles, adsorption resin ion adsorbent / Or pH buffer regulators such as amphoteric metal oxides and amino acids;

A3-5 modifiers include metal (hydroxide) oxides, carbonates, silicas, silicates, volatile non-toxic or slightly toxic alcohols and ester solvents, active groups containing metal elements, elemental carbon, and stable metals Powder, natural organic matter and its binder, synthetic resin and its binder, ultraviolet absorber;

A3-6 fillers include any inorganic or organic materials that are relatively inexpensive and inert (that is, they do not react directly with boron groups or intermediaries).

B. Reaction Synthesis Methods

The inventors have researched that the inorganic boride can easily form a boron group or a boronoxy group as a main structure or a key structure of an organic boron polymer with a large number of organic molecules in a hydroxy compound solution. In this condition, when the organic substance is a hydroxy compound or a hydroxy derivative (such as an ester), an organic boride having a boron group or a boronoxy group as a core structure and capable of crystal growth can be formed. The crystal formation conditions and growth The condition can be controlled by a variety of additives, such as base, acid and so on.

B1. In the present invention, a free solution of hydroxyl small and medium molecules (molecular weight of 2000) containing anhydrous or little free water is used. -Below 3000): In order to promote the copolymerization reaction of inorganic boride and various organic matters, the free liquid is both the medium and the reactant in the reaction, so as to realize the protective functional structure of the boride and organic matter to form a macromolecule (basic Mission). In order to increase the molecular weight of this protective function structure to form a functional structure level, the present invention adopts a reaction technology circuit that promotes the polymerization of organic substances with a boryloxy / boron group as the center. Therefore, a copolymerization reaction method and an auxiliary agent that are beneficial to molecular weight increase The present invention is suitable for use. On the other hand, in order to improve other physical and chemical properties of protective functional materials, especially applicable mechanical properties, the present invention also considers adding other additives or fillers. '

B2. According to B1, in the reaction synthesis method of the present invention, a substitution / ion exchange reaction, an esterification / ester exchange reaction, a crosslinking reaction, a coupling reaction, a polycondensation reaction and Synthetic method mainly based on copolymerization and supplemented by other reactions such as catalytic reaction.

C. Technical implementation plan

C1. First determine the reactants in the organic matter of A3-2 and select the corresponding organic intermediary reactants. One or more of the intermediary reactants can be selected in A3-3. Generally, according to the properties of A3-2 organic matter (one or two kinds / multiple types can also be considered), it is better to choose one to two kinds of A3-3, and the miscibility ratio of two kinds is 2: 8-8: 2. For example, If A3-2 determines the epoxy resins, then A3-3 should choose the corresponding alcohol amines; if A3-2 determines the half-mixture of hydroxymethyl cellulose and gelatin, then A3-3 chooses glycerin: ammonia solution = 6: 4-8: 2 blend.

C2. The H and 0 element ratios of organics should be fully considered in this choice. The general design H: 0 = 1.5: 1-3.2: 1 is more suitable, and it is best to be close to the 2: 1 ratio of water.

The selected mediation reaction should be distributed or co-melted and dispersed as much as possible in the liquid or soaking melting state. A3-1 Inorganic boride forms the initial organic boron active group:

-R.-BR,-• R.-BR, -R _r BR _2-

I J I

0- M OH (H)

M-0-B-R -0-B-R- (M) H-B-R- -O-B-O- 1 l t

OH (H) MM (OH / H) OH (0 / H / M) wherein R, R, and R ₂ are the same or different A3-3 groups, and M is a base or an inorganic group.

C4. Then, the active group is mixed with the determined A3-2 organic matter and forms a structure with backbone protection function by the synthesis method of B2 under certain conditions without the help of other ingredients or with the aid of auxiliary A3-4. Copolymer materials / products. C5. Corresponding to the initial reactive group of C3, the functional structure of the copolymer is

(bl) (b2) (b3)

(Pan-0-BR-D + + (R,) D _r OBR ₂ -D _2- (M) HBR-D +

I 1

OH (H) M M (OH / H)

(b4) (b5) (b6)

+ (R,) D _r OB- D ₂ (R ₂ ) +

OH (0 / H / M)

(7)

One of them has a macromolecular group or a block structure with two or more structures. In the structural formula, D, D, and D ₂ are the same or different organic macromolecular groups.

C6. If the above-mentioned copolymer contains the element N, the design technical scheme should consider the molar ratio of the element N: B <0.4.

C7. In order to improve the performance or produce specific demanded products, such as engineering structural materials, A3-5 modifiers can be added to the above copolymers to cross-link, homogenize, and so on. This process can be integrated in Structure with marginal protective function formed on the copolymer group

MC (bl) / …… / (b7) ^ MC MC-[(bl) / …… / (b7)] -MC MCf (bl) / …… / (b7)] -MC

(b8) (b9) (bO) family or family products. In the formula, [] is any one or two or more block groups in the structural formula (bl)-(b7), and MC is an A3-4 modifier group or the following filler molecular component.

C8. In order to reduce costs, you can also add A3-6 appropriate amount of fillers and mix them-that is, cheap stable metal (hydrogen) oxides, silicates, high molecular carbohydrates, glass fibers, carbon powder and other substances.

C9. According to C1-C8, the measurement range of the embodiment is as follows:

C9-1 According to the nature of A3-2 organic matter, choose one or more of A3-3 intermediate reactants to take 50-200 parts by weight, preferably in the range of 20-100 parts by weight;

C9-2 A3-1 one or more inorganic borides are taken in an amount of 10-120 parts by weight and blended / melted with the above amount, preferably in a range of 20-100 parts by weight;

C9-3 A3-2 organic matter powder 5-200 parts by weight with the above-mentioned melt (dissolved) each component are blended and copolymerized, the preferred range is 20-150 parts by weight; C9-4 A3-4 additives take one or two parts of 0-50 parts by weight;

C9-5 A3-5 modifier takes one to a plurality of 0-100 parts by weight, preferably one or two 5-80 parts by weight;

C9-6 A3-6 filler takes one or two total 0-300 parts by weight, less 5-230 parts; C9-7 soaking takes 50 'C-270 V according to the characteristics of the copolymerization reaction, the pressure is the reaction It is advisable that the material does not vaporize. Within the scope of measurement, the protective functional material of the present invention can be made with any applicable amount according to the actual protection needs. '

In the preparation of the above-mentioned organic boron polymer having a protective function, a catalyst, a shrinkage promoter, an ion adsorbent, and a pH buffer adjuster may be used to generate the derivative, and the main reaction thereof is a substitution reaction or an ion exchange reaction, and a cross-linking reaction. Coupling reaction, copolymerization reaction and mixing method without chemical change and cross-bonding fusion method.

In one embodiment, the organic boron polymer having a protective functional structure of the present invention is prepared using the following components: a) 10-120 parts by weight of an inorganic boron polymer; b) 50-200 parts by weight of an intermediate reactant; c) an organic substance 5-200 parts by weight; d) additives 0-150 parts by weight; e) modifiers 0-100 parts by weight; f) fillers 0-300 parts by weight.

Of the above components, preferably a) 20 to 100 parts by weight of a boride selected from the group consisting of aluminum boride (zinc / titanium / magnesium), boron oxide, alkali (earth) metal borate, alkali (earth) metal metaboric acid One or two of anhydrous sodium (potassium) tetraborate, ammonium pentaborate, sodium (potassium) borohydride, sodium (potassium) perborate; b) 70-150 parts by weight of intermediate reactants, selected from ammonia , Liquid alcohol, sodium (potassium) ethoxide (di),. One or two of fatty acids above ₂ , esters above C ₃ and C ₂ -C ₆ alcohol amines; c) 10-150 parts by weight of organic matter, selected from polymer fats, non-toxic or low-toxic alicyclic compounds And one or two of its derivatives, alginic acid, rosin, gelatin, oxygen-containing synthetic resin and its binder; d) the auxiliary is selected from one of tetrabutyl titanate and aluminum isopropylate 0-S parts by weight, or one of sodium hydroxide, silicon oxide, boron oxide, and calcium oxide, 0-30 parts by weight, or white carbon black, activated white clay, activated carbon powder, silicon ultrafine particles, acrylic resin One is from 0 to 30 parts by weight, or one of alumina powder and aminoacetic acid is from 0 to 30 parts by weight; wherein a + b + c + (d) is used to synthesize a prepolymer product at any ratio specified or re- With or without adding e) 5 to 80 parts by weight of a modifier selected from the group consisting of alkaline earth metal (hydrogen) oxides, sodium lauryl oxide, aluminum oxide, ammonium carbonate (hydrogen) carbonate, silicon oxide, and alkaline (earth) metal silicic acid Salt, ethanol or ethanol ethyl (propyl) ester solvent, titanate coupling agent, aluminum grinding fine powder, activated carbon and Fibers, liquid natural rubber, epoxy resin, fiber resin, U compound One or two of them; f) 5 to 230 parts by weight of a filler, one or more selected from inexpensive stable metal (hydrogen) oxides, silicates, high molecular carbohydrates, glass fibers, carbon powder, or the like Two types; f and g are uniformly distributed in the prepolymer of a + b + c + d to form a derivative product of functional protective copolymer.

Alternatively, preferably a) 30 to 100 parts by weight of a boride selected from zinc boride (magnesium / aluminum), boron oxide, sodium borate (potassium), sodium metaborate (potassium), anhydrous sodium borate (potassium), five -One or two of ammonium borate and sodium borohydride; b) 80-120 parts by weight of an intermediate solution, selected from the mass ratio of ammonia solution to ethanol (liquid alcohols such as ethylene glycol, glycerol, etc.) 3: 7-7: 3 , Mass ratio of sodium (potassium) ethanolate to ethanol (liquid alcohols such as ethylene glycol, glycerol) 3: 7-5: 5, liquid fatty acids, acetates, liquid fatty acids (> C ₂ ), triethanolamine, (two C) One or two of isopropanolamines; c) 20-80 parts by weight of organic matter, selected from soybean oil, limonene, pinene, linalol, alginic acid, gelatin, polyester resin, polyetherketone Resin, epoxy resin, or one of oxygen-containing resin in silicone resin or two kinds of oxygen-containing resin and oxygen-free resin mixed; d) the auxiliary agent is selected from 0 to 5 parts by weight of tetrabutyl titanate, or silicon, One of boron and calcium oxide is 0-20 parts by weight, or white carbon black, activated clay, acrylic adsorption One of the fats is 0-25 parts by weight, or one of the alumina powder and aminoacetic acid is 0-20 parts by weight; wherein a + b + c + (d) is reacted to form a prepolymer product according to the description, Or e) 10-40 parts by weight of a modifier selected from the group consisting of alkaline earth metal (hydrogen) oxides, sodium antimonate, alumina, ammonium (hydrogen) carbonate, silicon oxide, alkaline (earth) metal silicates, ethanol Or one or two of ethanol ethyl (propyl) ester solvent, titanate coupling agent, aluminum grinding fine powder, activated carbon and carbon fiber, natural rubber liquid, epoxy resin, fiber resin, UV-based compound; f) 5 -150 parts by weight of filler, one or two selected from inexpensive stable metal (hydroxide) oxides, silicates, high molecular carbohydrates, glass fibers, carbon powder, etc .; f is evenly distributed in the prepolymer Derivatives that form functional protective copolymers

□ According to the dynamic working principle of adaptive thermal decomposition, the protective functional material of the present invention is suitable for comprehensive protection in multiple fields and multiple uses, and has the following superior performance and good effects than the existing static protective materials:

1.High temperature insulation performance

When the functional structure (bl) /-/ (M0) encounters a high temperature above 250 ° C-1000 'C, the structural change of the organic thermal decomposition gradually occurs with the temperature rise

> 700 ° C,

+ 0, -ΐ θ-Β-0-Ι ₂ -ϋ ₂ + (or other formula) → + R-0-B-0-R + + nH ₂ 0 (steam)

-B-0-C-/-BC- + mH ₂ 0 (steam) (b 11) In this change of organic structured water (ie, OH, 0, and H groups), a large amount of generated water loses most of the heat radiated to the material and its changed structure, and at the same time, the water vaporizes to form the material. Micropores are hollow. The microporous high temperature (> 2000 'C-3000' C) structure is easy to promote the good performance of vacuum insulation with low gas density in the condition of high temperature> 500 'C. This vacuum can theoretically be maintained at about Atmospheric density of 0.2%. When the temperature is between 1000 'C-3000 ° C, the thermal decomposition change of the above formula will change faster with higher temperature. Experiments have shown that high-temperature thermal insulation performance is at least 1-2 orders of magnitude lower than existing low thermal conductivity materials. In contrast, we can only call the prior art products insulation materials.

2. High temperature oxidation resistance

The main reason is that the boron group or boron carbon / boron oxycarbon group in the functional structure has a high temperature anti-oxidation catalytic ability above 700 'C-1500' C. Experiments have shown that this anti-oxidation ability is still apparent under the high heat of 3000 'C-4500' C in the air.

3. The working principle of thermonuclear fire

In the runaway high temperature of a thermonuclear accident, the formed water vapor on the one hand loses a large amount of energy, and on the other hand, the (M l) -type inorganic component formed by coking / carbonization absorbs thermal neutrons to prevent the thermonuclear reaction from continuing. The nuclear shielding material in the modifier also has a certain ability to absorb and protect-comprehensively, when the energy of the thermonuclear reaction increases and the neutron proliferation is less than the loss and absorption value, it will be blocked, which can achieve the purpose of nuclear fire protection.

4. High-energy beam impact resistance

When the functional structure of the material encounters a high-energy beam impact above 1800 'C-4000' C, such as a laser beam (up to 10,000 degrees to 100 million degrees), the rapid evaporation of structured water forms a few hundred to several tens. Ten thousand atmospheric high-pressure dynamic air cushions caused a sharp decrease in high-energy impact forces in the direction of high-energy transmission gradients. At the same time, materials such as the carbonized layer of organic matter absorb a small part of the energy transmitted through and vaporize, and form an internal high-pressure layer. In the internal high-pressure layer (such as -β-0-C), the formation of complex high-temperature resistant materials, As a result, the functional protective material has better resistance to high-energy impact than steel, ceramics, and the like. Experiments have shown that this performance is several times to several tens of times higher than that of hard steel in the high heat of oxyhydrogen flames, and the higher the temperature, the better its performance.

5. Other performance and indicators

Experiments show that the organic boron polymer material provided by the present invention with dynamic adaptive protection function has comprehensive advantages that are incomparable with the products of the prior art. For example: US93-5272237 is suitable for making changes between 600'C-1000'C, and the present invention is suitable for making changes above 500'C-2000'C; US85-4504611, Ping 7-41611 and Ping 7-278267 are best to achieve V-0 flame retardancy, and the organic boron polymer material of the present invention is preferably non-flammable above 1000 'C-2000' C--by the method of the present invention Generally, the flame retardancy of the material can be self-extinguished within ≤ 3-5 seconds, while the average of flat 7-4161 1 embodiment is 12.8 seconds. In addition, the total components of the present invention do not contain halogen, sulfur, phosphorus, arsenic, heavy metals and radioactive elements that are toxic or pollute the environment. The present invention has good environmental benefits throughout the process.

In short, the biggest difference between the organic boron polymer provided by the present invention and the prior art is that the present invention utilizes adaptive changes in the organic protective function structure in the material to correspond to various changes in the external environment; Allergies change. The former has a limitless protective performance, and the latter has only a certain amount of static indicators and protective performance.

The experimental research on the two types of boron polymers shows that (1) the protective material with functional structure provided by the present invention has crystals grown in the main functional structure of dendritic (three-dimensional) and various snowflake-shaped ( Most of the planes), crystalline composite materials with marginal functional structures are mostly skin-like, cream-like, shrinking hilly, and solid and oily without obvious appearance characteristics; (2) Burning quality after 800-1200 'C The loss method determines that the protective material with a functional structure of the present invention contains 50%-80% of the structured water and the combined water according to different reaction conditions, and the combined water and structured water of the present invention for high-temperature protection is generally Less than 36%; (3) The product of the present invention is 200%. Below C-300 'C, the combined water is mainly lost, and above 300 ° C-350 ° C, structural water is initially lost, 600 ° C. C-700 'C transitions from organic polymers to inorganic polymers after most of the main structural water is lost, 800 ° C. From C-900 'C to boron carbide and inorganic boride, 1500 ° C-2000' C from inorganic polymer to glassy state; (4) gradually heating the surface of the crystal of the present invention, loss below 200 -C-300 'C Water can be reversed and recombined with water. 300 'C-350' C can be dehydrated and discolored and cannot be completely recovered. 600 'C-750' C is tan for a long time (the performance of boride containing). Change from 800 to C-900 'C from tan to dark brown (black is mainly manifested by the carbonization of organisms), 800 V-1200 ° C crystals are easier to separate from wood materials to hard to separate from carbonized layer and carbonized The layer is flammable, indicating the formation of high-molecular boron carbide; (5) The crystal of the present invention contains a large amount of structured water and crystalline water, and a variety of raw materials containing ionic bond compounds such as borax in each proportion of the material do indeed produce a polymerization reaction-each ionic group The agglomerates together form an integral part of the product of the invention.

Best Mode for Carrying Out the Invention

According to the preparation method, the present invention starts from the economic and technological optimization scheme, and the best way can achieve better results by controlling as follows: ① H: 0 = 1.8: 2.3: 1, Ν: Β <0.2;

② Aqueous solution reaction adopts temperature controlled conditions of 80 ° C-95 ° C, and organic polymerization reaction adopts reaction method containing alcohol or ester as carrier;

③ B: C≥1 is generally required in boron polymers. When B: C> 1, the content of structured water and bound water should be ≥50%;

④ The reaction residue is used as a filler for the application material.

The present invention is explained in detail by the following examples.

Example 1

Fire retardant decorative coating

Take boric acid: sodium metaborate in a ratio of 1: 9, the total amount is 50 parts by weight, add 70% by weight of 3% pentaerythritol aqueous solution, and add the same amount of sucrose and starch, a total of 10 parts by weight, and then heat to 80 ■ C-100 'C Stir in uniform temperature, after fully cooked and uniform, then do the following technical treatment according to different decorative effects:

a. Transparent paint, directly spray the reaction mixture at 70 'C or higher for 2-3 times, and spray it again after each natural drying, and finally dry or dry naturally;

b. Add 10 parts by weight of sodium silicate modifier to the waste heat, make the coating product after the homogeneous reaction, spray 1 or 2 times in 50 'C-70' C preheating, dry naturally with frost or small snowflakes, 3 Five times of natural dryness and large snowflakes;

c. Matte / star light paint, add 30-55 parts by weight of quartz sand or aluminum hydroxide small crystallized with other insoluble crystal sand in the remaining heat, stir evenly, pre-heated or not pre-heated by hand coating 1-3 mm, After natural drying, it has a matte decorative effect-if the selected crystal sand has more optical surfaces, it can show a starlight effect; d.-General coating, add 25 parts by weight of magnesium hydroxide (calcium) in the residual heat or Aluminum hydroxide 60-

100 mesh powder, pre-heated or not pre-heated, coated with 2-3mm, it is ordinary white effect. If various pigments are added, it can have various colors:

Various a-d decorative coatings are suitable for ordinary fire and flame retardants below 200 ° C and their comprehensive applications. Example 2

High temperature insulation

Take 40 parts by weight of boric acid or sodium tetraborate pentahydrate, add 60 parts by weight of a 2% sorbitol aqueous solution, add 20 parts by weight of monosaccharide and starch, and then add 90 parts. The curing reaction under C-100 'C conditions, using waste heat to add 5-10 parts by weight of white carbon black auxiliary, and after mixing, add 20-50 parts by weight of alumina or Titanium oxide powder was mixed with a mixer. The reactant is preheated to a temperature of 60 ° C and a flowable thick substance, and it is a solid at room temperature. The temperature of 350'C-500'C and above is dehydrated to form a porous thermal insulation material.

a. For energy-saving applications in high-temperature metallurgy, preheat 70-80 'C cast for insulation shirt wall use; b. If used on metal structures, 5-15 parts by weight of epoxy resin and its curing agent can be added; c For applications such as building fire doors, it can be added with 10-30 parts by weight of resin adhesive to make boards or directly attached to metal walls.

Example 3

High-temperature antioxidant materials

Take 0.5: 9.5-1: 9 ratio of aluminum boride powder: 50 parts by weight of anhydrous sodium tetraborate, add 80-100 parts by weight of water, and then add the same amount of sucrose · starch 15-27 parts by weight or equivalent 5-15 parts by weight of sucrose · hydroxycellulose, 100 'C bath heat uniformity. According to different uses, do the following technical treatments: a. Make flammable product protective layer (such as decorative board). Add 5-15 parts by weight of fumed silica, mix and mix well, then preheat spray or manual coating at room temperature 2-5mm, and dry or dry naturally;

b. As a metal protective layer (such as aluminum profile), add 5-15 parts by weight of silicone oil and 5-10 parts by weight of epoxy resin or polyurethane adhesive, mechanical coating or manual coating, 80 'C-230 ° C baking dry.

a-b can be used for insulation applications above 2000 'C-3000' C and its comprehensive application of high temperature protection in about 5-100 minutes.

Example 4

Ray absorbing and shielding materials

In the initial basic products of the above embodiments, adding an appropriate amount of aluminum powder, silicon powder, boron powder, or a small amount of activated carbon powder filler is suitable for the requirements of radiation absorption and shielding.

Example 5

Nuclear radiation shielding material

In the above-mentioned basic products of various uses, 5 to 10 parts by weight of an equal amount of boron nitride and carbonized fiber are added to the resin adhesive in an amount of 5 to 20 parts by weight, so that it can be used as a core shielding solid material. In Example 1 -3 basic products, adding 900 'C-1500' C residues of the present invention burning in the air, that is, a complex solid mixture containing NB and CB (high molecular) as the main component 10-30 parts by weight as a filler, That can be used as ointment-like core shielding filling material.

Example 6 High energy beam impact resistant material

Take 50 parts by weight of any kind of alkali metal borate, and take 15 parts by weight of sucrose: mash with 6: 4, mix with 80 parts by weight of water, add about 5 parts of gum arabic after heat curing at about 100 ° C, and mix until mature. Then, 40 parts by weight of equal amounts of aluminum hydroxide, magnesium trisilicate, and an appropriate amount of titanium oxide powder are mixed with the waste heat, pressed and formed, and naturally dried into a finished product.

This product is mainly used for high energy impact resistance below 10000 'C and other comprehensive protection. Above 10000 'C, its breakdown resistance is also better than steel. Experiments have shown that oxygen-hydrogen torch cutting at about 3500' C proves that its breakdown resistance is about 20 times that of carbon steel.

Example 7

Laser and solar wind resistant materials

100 parts by weight of the base maturation solution of Example 6 were mixed with 50 parts by weight of magnesium trisilicate using the residual heat, and then 30 parts of ultrafine aluminum silicate was added into the 30-60 ° C residual heat, mixed and ground, and then Compression molding, natural drying for finished products.

This product is mainly used in laser strikes and the impact of high-energy particles in the universe and its comprehensive protection applications. For example, the hard solid material made of this material has a resistance to 3500 'C hydrogen-oxygen flame torch strikes as in Example 6. About 1.5 times, which is 30 times that of ordinary steel.

Example 8

Thermal insulation fire retardant transparent coating

In this embodiment, a method for preparing an alcohol solvent at normal pressure and normal temperature is used to prepare a heat-insulating, fire-retardant and flame-retardant transparent coating of an organosilicon functional structure copolymer.

According to the weight ratio, take 35 parts of boron oxide powder and mix in 120 parts of ethanol (content> 96%), and then mix with 50 parts of silicone glass resin and 5-15 parts of non-toxic solid alcohol (such as pentaerythritol cross-linking agent). That is to obtain a transparent fire-resistant coating. Among them, 1 to 2 parts of an alkali metal compound such as sodium borate, 1 to 5 parts of an antimony oxide or an alkali metal antimonate flame retardant modifier can also be added. In this case, the fire and flame retardant effect on 5-15mm thick wood boards has reached the national standard B1.

Example 9

Fire-resistant anti-radiation coating

In this embodiment, an epoxy resin functional copolymer is prepared by esterification, and is mainly used as a fire-resistant and radiation-resistant coating for rubber, plastic, wood, and metal. According to the weight ratio, take 30 parts of boric acid, dissolve in 100 parts of glyceryl ether, and add 30 to 50 parts of glycidyl ester epoxy resin. Add 5 parts of borax and 10 parts of boron oxide high temperature curing agent, and you can also add 1-2 parts of white carbon black curing aid, that is, a boron-poly coating that forms a functional junction (bl), (b3) or (b7). According to the color requirements of the coating, add an appropriate amount (such as 30-50 parts) of stable metals or metal oxides and carbon substances to the copolymer, such as silver-white aluminum powder, white titanium oxide powder, yellow iron oxide, and black Activated carbon powder and so on. The coating is cured by irradiation or baking during use. The experiment proves that this coating adheres to the protected article with a thickness of 0.1-1mm, which not only has the shielding effect on β, γ and α, but also has a good high temperature fire protection effect below 3500 'C.

Example 10

Adiabatic fire-resistant anti-radiation engineering materials

This embodiment is prepared by copolymerization to prepare an epoxy functional structural engineering material, which is used as an adiabatic, fireproof and radiation resistant engineering material.

According to the weight ratio, 50 parts of ammonium pentaborate is crushed to 80-150 mesh and mixed with 10 parts of fumed silica, and then uniformly distributed in 50 parts of glycerin and then mixed with 100 parts of liquid alicyclic epoxy resin, wherein Add 10-25 parts of alcohol amine curing agent and 1-5 parts of magnesium, beryllium, aluminum and other powder nuclear shielding modifiers. If a solid alicyclic epoxy resin is used, add 20-70 parts of diacetone alcohol diluent, and then add ammonium pentaborate, glycerol and the like. This formulation is molded into products at 80 'C-150' C. The fire and radiation resistance of this material is similar to that of Example 9. At high temperatures, it is easier to produce expanded microporous bodies than the material of Example 9.

Example 11

Anti-oxidation flame retardant and radiation protection material

In this embodiment, a method for copolymerizing with fiber articles is used to prepare materials that are specially used for immersion in wood, polymer fiber materials, or composite microporous materials to play the role of oxidation resistance, flame retardancy, and radiation protection.

According to the weight ratio, take 50 parts of sodium perborate and dissolve in 150 parts of organic acid. In order to increase the solubility of boride, it can also be dissolved in a homogeneous solution of 150 parts of isopropanolamine and 30 glycerol. Then, the article is immersed in this solution for infiltration treatment. The processing time is generally measured in hours according to the volume and surface area of the article, and then taken out at 70'C-130'C for about 1-2 hours. This treatment method is suitable for fire and flame retardant applications below 1500 'C.

Example 12 Thermal insulation and nuclear radiation shielding material

High-molecular multi-functional structural materials or coatings are specially used for long-term thermal insulation and radiation shielding.

According to the weight ratio, take 100 parts of boric acid or anhydrous sodium tetraborate containing boric acid (20%-30%), sodium (meta) borate and 20-30 parts of aluminum boride powder are not homogeneously mixed, and then in an appropriate amount of ethanol or Acetic acid ester, α-allyl glyceryl ether auxiliaries are mixed with 100 parts of the cross-linking agent polyester polyol or polyether polyol with the participation of 2 to 5 parts of BN powder to form (bl)- b7), which is a functional structure group of glycans, which is pre-polymerized with 30 parts of polyphenyl ester or polyhydroxy ether to form a block copolymerized functional structure semi-finished product. Then

a. For engineering materials, 100 parts of the prepolymer and 60 parts of aliphatic epoxy resin and 10 parts of carbon fiber are all mixed and cured by compression molding under the conditions of 100'C-250'C. -Before curing, you can add low cost A3--6 filler;

b. For coating, you can add a small amount (such as 100 parts plus 10-20 parts) of metal oxide and increase the amount of auxiliary to make the required coating.

c. It is also possible to use a hydrophobic silica filler or fumed silica in an amount of 10% and 50 parts of the silicone resin to form 100 parts of the semi-finished product with a high temperature resistance copolymer.

The invention is likely to have many additional modifications, enhancements, and changes based on the above discussion. Therefore, it should be understood that the present invention may be implemented in ways other than those specifically described herein. The scope of the invention is defined by the claims appended hereto and is not limited to the embodiments set forth above.

Claims

Rights request

1. A material of a boron polymer having an adaptive protective function structure, characterized in that the material has a main structure with a boron group or a boroxy group as the center and an organic active group, and has a total weight of the material. 50-80% structured and bound water; of which

The structured water refers to all H and 0 elements in the functional structure of the material, and the content ratio is

1.6: 1-2.5: 1.

2. The material according to claim 1, wherein the main structure composed of a boron group or a boronoxy group and an organic active group contains one or more of the following structural units:

{Sc-B-Sc}-, -Sc-B-Sc-R _: M-Sc-B-Sc-quasi) RB-Sc-R (M)

M (OH / H)

(al) (a2) (a3) (a4)

+ Sc-0-B-0-Sc + R, -Sc-0-B-0-Sc-R, (M) M-Sc-O-B-O-Sc-R (M)

I a

OH (O) OH (O)

(a5) (a6) (a7)

M-O-B-O-Sc-R (M) M-B- (0) -Sc-R (M) (M-B) `` Sc-OH (O) OH (0 / M) n = l ~ 120

(a8) (a9) (alO)

Sc is a glycosyl;

R, R, and R ₂ are an oxygen-containing organic group or a fluorene hydrocarbon group;

M is a base or other inorganic root J

3. The material according to claim 2, wherein the main structure further contains one or more of an auxiliary agent, a modifier, and a filler to form a marginal functional structure having the following general formula:

MQ (l) / …… / (10)-] MC MC '[(1) / …… / (10)] -MC MC "E ~ (1) / …… / (10)]' MC

(al l) (al2) (al3) where

The filler is selected from alumina, aluminum hydroxide, aluminum compounds, titanium oxide, titanium hydroxide, magnesium hydroxide, calcium hydroxide, poorly soluble silicates and carbonates, silicon powder, boron powder, and carbides. , One or more of the group consisting of insoluble carbohydrates, natural adhesives, halogen-free, sulfur-free synthetic resins and their adhesives.

4. The material according to claim 1, wherein the main structure composed of a boron group or a boronoxy group and an organic active group contains one or more of the following structural units:

-D ₂ +

(bl) (b2) (b3)

(H) M-O-B-R-D-f + (M) H-B-R-D +

OH (H)

M (0 Li)

(b4) (b5) (b6)

-(R D.-O-B- D ^ R,)-^

OH (0 / H / M)

(b7)

R, R, and R ₂ are the same or different oxygen-containing organic groups;

M is a base or an inorganic root.

5. The material according to claim 4, wherein the main structure further contains one or more of an auxiliary agent, a modifier, and a filler to form a marginal functional structure having the following general formula:

MC- (l) / …… / (17)-]-MC MC-[(1) / …… / (17)] -MC MC + (1) / …… / (17)] -MC

(b8) (b9) (blO) where

MC is a stabilizing group of a modifier or stabilizer;

The filler is any inorganic or organic substance that does not directly react with boron-based or ammonia liquids, alcohols, alkali metal alcoholates, aliphatic carboxylic acids and derivatives thereof, and alcohol amines.

6. A method for preparing a boron polymer material with an adaptive protective function structure, characterized in that a substance having a hydroxyl group, an aldehyde group or a ketone group is reacted with an inorganic boride to generate a compound having a boron group or a boronoxy group. As the center, it constitutes a main structure with organic active groups, and has structured water and bound water which account for 50-80% of the total weight of the material;

The structured water refers to all H and 0 elements constituting the functional structure of the material, and the content ratio is close to 1.6: 1-2.5: 1;

7. The method according to claim 6, wherein the substance having a hydroxyl group, an aldehyde group or a ketone group is selected from the group consisting of monosaccharides, disaccharides, trisaccharides, polysaccharides, sugar acids and their metal salts, and ammonium sugar acid. One or more sugars in the group consisting of salt, water-soluble cellulose and its salts, and sugar (organic) organic cellulose,

8. The method according to claim 7, wherein the reaction is performed in water or an aqueous solution containing an alcohol and an alcohol derivative, and the alcohol or alcohol derivative is selected from the group consisting of ethanol, ethylene glycol, glycerol, and pentaerythritol. , One or more of the group consisting of sorbitol.

9. The method according to claim 7 or 8, characterized in that the method further comprises adding a human assistant, a modifier, a filler to form a derivative having a marginal functional structure,

MC- (l) / …… / (10HMC MC '[(1) / …… / (10)] -MC MCf (1) / …… / (10)] -MC

(al l) (al2) (al3) its towel, MC is a stabilizing group of a modifier or stabilizer;

The auxiliary agent is selected from one or two selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, silica, and non-toxic organic acids;

The modifier is selected from the group consisting of alkaline earth metal hydroxides, fourth cycle metal oxides, fourth cycle metal hydroxides, antimony and tin compounds, ammonia or alkali metal silicates, alkali metal carbonates, and alkali metals. One or two of the group consisting of organic acid salts, gum arabic, and active silica;

The filler is selected from alumina, aluminum hydroxide, aluminum compounds, titanium oxide, titanium hydroxide, magnesium hydroxide, calcium hydroxide, poorly soluble silicates and carbonates, silicon powder, boron powder, carbonization One or more of the group consisting of substances, insoluble carbohydrates, natural adhesives, synthetic resins containing no halogen / sulfur / phosphorus elements and their adhesives.

10. The method according to claim 6, wherein the substance having a hydroxyl group, an aldehyde group or a ketone group is selected from the group consisting of oils and fats, aliphatic compounds and derivatives, organic polymers and salts thereof in natural plants and animals. One or more organic substances in the group consisting of, synthetic resin, and oxygen-containing synthetic resin.

11. The method according to claim 10, wherein the reaction is performed in the presence of a hydroxy organic substance and its derivative or an aliphatic hydroxy acid or an alcohol or ammonia.

12. The method according to claim 10 or 11, characterized in that the method further comprises adding an auxiliary agent, a modifier or a filler to form a marginal functional structure.

MC- (l) / …… / (17) + MC ΜΟ · [(1) / …… / (17)] -MC MC- (l) / …… / (17)] -MC

(b8) a derivative of (b9) (blO); wherein,

MC is a stabilizing group of a modifier or stabilizer;

The auxiliary agent is selected from the group consisting of metal organic catalyst, silicon oxide, boron oxide, alkali metal hydroxide, alkaline earth metal oxide shrinking agent, alkaline earth metal silicide powder, carbon powder, semiconductor elementary ultrafine particles, adsorption resin ion adsorbent, amphoteric metal oxides, such as amino acids _P H buffer one of the group consisting of regulator or more;

The modifier is selected from the group consisting of metal oxides, metal hydroxides, carbonates, silicon oxides, silicates, volatile non-toxic or slightly toxic alcohols and ester solvents, active groups containing metal elements, elemental carbon, One or more of the group consisting of stabilized metal powder, natural organic matter and its binder, synthetic resin and its binder, and ultraviolet absorber; The filler is any inorganic or organic substance that does not directly react with boron-based or ammonia solution, alcohols, alkali metal alcoholates, aliphatic carboxylic acids and derivatives thereof, and alcohol amines.

13. A boron polymer material with a protective function structure according to claim 2 or 3 and a boron polymer material with an adaptive protective function structure prepared by the method of one of claims 7 to 9 are prepared a) 200 -C- 3500 'C high temperature insulation; b) 300' C-4500 'C high temperature oxidation resistance; c) 350' C-5000 'C fire and flame retardant; d) 2500' C-10000 'C above high energy beam impact resistance; and e) 2000 'C-3000: The following thermonuclear control and its application in fire protection and shielding products.

14. The boron polymer material with protective function structure according to claim 4 or 5 and the boron polymer material with adaptive protective function structure prepared by the method of one of claims 10 to 12 are prepared a) 260'C- 2700 'C high temperature insulation; b) 350 ° C-3500' C high temperature anti-oxidation; c) 400 'C-4500' C fire retardant; d) 1800 'C-5000' C and above products with high energy beam impact resistance application.

15. Application according to claim 13 or 14, characterized in that said products are industrial filling materials, (forest) fire fighting materials, engineering structural materials and decorative materials.