CN107987312A - A kind of preparation method of light stabilizer, light aging resisting PP composite material - Google Patents

Abstract

The invention relates to a preparation method of a novel light stabilizer and a light aging resistant polypropylene composite material with the light stabilizer obtained by the preparation method. The general formula of the light stabilizer obtained by this preparation method is expressed as [M(II) _1-x M(III) _x (OH) ₂ ] ^x+ A _x/n ^n- mH ₂ O, wherein, M(II) are divalent metal ions Mg ²⁺ and Ni ²⁺ , M(Ⅲ) is trivalent metal ion Al ³⁺ , A is an anion whose valence is ‑n, and x is M(Ⅲ) and [M(Ⅲ)+ The molar ratio of M(II)], m is the amount of crystal water, x=0.1～0.5, A is OH ^‑ , CO ₃ ^2‑ , m=0～10. The invention solves the problem that an organic ultraviolet absorber needs to be inserted between layered double hydroxide layers in order to obtain a light stabilizer, so as to obtain a light-aging-resistant polypropylene composite material with good stability.

Description

A kind of preparation method of light stabilizer, light-aging resistant polypropylene composite material

technical field

The invention belongs to the technical fields of material chemistry and chemical industry, and relates to a preparation method of a light stabilizer and a light-aging resistant polypropylene composite material with the light stabilizer.

Background technique

Polypropylene (PP) is widely used in engineering fields such as chemical engineering, building materials, vehicles and ships because of its advantages such as heat resistance, easy processing, and light weight. The current development trend of PP materials shows that PP is widely used outdoors, such as outdoor decoration materials, auto parts, plastic seats for stadiums, etc. However, as a polymer material, PP, like other polymers, will change when exposed to outdoors for a long time, such as cracks on the surface of the product, loss of gloss, yellowing, and a decrease in relative molecular weight. More seriously, it will lead to impact strength. , Elongation at break, tensile strength, bending strength and other mechanical properties are greatly reduced, which affects the normal use of PP products. PP exposed to outdoors will accelerate aging, and there are many factors that cause aging. Temperature, precipitation, humidity, pollutants and ozone in the atmosphere can all cause material aging. However, the main reason for aging is that the PP material absorbs the energy of ultraviolet light, triggering an automatic oxidation reaction, which leads to photodegradation, which makes the local appearance and physical and mechanical properties of the product deteriorate. Therefore, there is an urgent problem to be solved: the PP material used outdoors must have certain anti-ultraviolet aging properties. Therefore, PP materials with anti-ultraviolet aging function have become a hot research topic at home and abroad. In order to obtain a polypropylene composite material with better aging resistance, people often improve its weather resistance by adding stabilizers and antioxidants. This method is relatively simple and feasible, and it is also the most practical and widely used method at present, and Good results have been achieved.

At present, the research on layered metal hydroxide light stabilizers mainly focuses on the replacement of interlayer anions, and the introduction of anionic interlayer materials such as salicylates, benzophenones, and hindered phenols, so as to obtain layered metal hydroxide light stabilizers. There are few reports on the preparation of layered double hydroxide light stabilizers with high stability and strong ultraviolet light absorption ability by changing the element types and ratios of the cationic laminates.

Contents of the invention

The invention provides a preparation method of a light stabilizer and a light aging resistant polypropylene material with the light stabilizer.

A preparation method of a light stabilizer, the general formula of the light stabilizer is expressed as [M(II) _1-x M(III) _x (OH) ₂ ] ^x+ A _x/n ^n- mH ₂ O, wherein , M(Ⅱ) is divalent metal ion Mg ²⁺ and Ni ²⁺ ; M(Ⅲ) is trivalent metal ion Al ³⁺ ; A is an anion whose valence is -n; x is M(Ⅲ) and [ The molar ratio of M(III)+M(II)]; m is the number of water of hydration, x=0.1-0.5, A is OH ^- , CO ₃ ^2- , m=0-10; the preparation method includes the following steps:

A. Dissolve the soluble salts of divalent magnesium ions, divalent nickel ions and trivalent aluminum ions in water to prepare a salt solution with a cation concentration of less than 1.0mol/L, wherein the molar weight of divalent cations is greater than 60% of the total molar weight of cations %;

B, adding urea to this salt solution to obtain a mixed solution, wherein the molar concentration of urea is 0.5 to 3.0 times the molar concentration of divalent metal cations;

C. Transfer the mixed solution to a reaction kettle, and cool to room temperature after hydrothermal reaction for 0.5h-48h, filter, wash, and dry the washed product to obtain the light stabilizer described in claim 1.

Further, the range of cation concentration in step A is 0.1mol/L-1.0mol/L.

Further, the molar weight of cations in the step A is greater than 80% of the total molar weight of cations.

Further, the molar concentration of urea in the step B is 1.0-2.0 times the molar concentration of divalent metal cations.

Further, the hydrothermal reaction temperature in step C is 100°C-200°C.

Further, the drying condition of step C is 80°C to 120°C for 4h to 12h.

A light-aging resistant polypropylene composite material, the light stabilizer prepared above is added to polypropylene, and after mixing, the light-aging resistant polypropylene composite material is obtained, wherein the mass fraction of the light stabilizer is the total mass fraction of the composite material 0.05% to 10% of that.

Compared with the prior art, the present invention has the following advantages:

1. The process is simple, the operation is convenient, the process is short, the production cost is low, and the requirements for equipment materials are low;

2. In the reaction process, it is possible to produce magnesium-nickel-aluminum-containing light stabilizers and polypropylene light-resistant aging composite products without adding additives, anionic ultraviolet absorbers, and blocking agents.

Description of drawings

The present invention will be further described below in conjunction with accompanying drawing and embodiment, in the accompanying drawing:

Fig. 1 is the XRD spectrogram of the light stabilizer of embodiment 1 of the present invention

Fig. 2 is the XRD spectrogram of the light stabilizer of embodiment 2 of the present invention

Fig. 3 is the XRD spectrogram of the light stabilizer of embodiment 3 of the present invention

Fig. 4 is the SEM picture of light stabilizer of embodiment 4 of the present invention;

Fig. 5 is the XRD spectrogram of the light stabilizer of embodiment 4 of the present invention;

Fig. 6 is a graph showing the relationship between aging time and tensile strength of the light-aging-resistant polypropylene composite material in Example 4 of the present invention under different additions of light stabilizers.

Detailed ways

The present invention will be further described below in conjunction with embodiment.

Example 1

The salts of soluble divalent and trivalent metal cations used are magnesium nitrate hexahydrate (Mg(NO ₃ ) ₂ 6H ₂ O), nickel nitrate hexahydrate (Ni(NO ₃ ) ₂ 6H ₂ O) and nitric acid nonahydrate Aluminum (Al(NO ₃ ) ₃ .9H ₂ O).

Weigh 5.77g of magnesium nitrate hexahydrate, 6.54g of nickel nitrate hexahydrate and 12.66g of aluminum nitrate nonahydrate into a 200mL beaker, add 150mL of secondary water, and stir to dissolve them completely.

Weigh 12.16g of urea (H ₂ NCONH ₂ ), add it into the salt solution, transfer it into a hydrothermal reaction kettle after being completely dissolved, and react at 140°C for 8h.

After taking it out, cool it naturally, filter, wash, dry in a constant temperature blast drying oven at 80°C for 8 hours, grind, and sieve to obtain a magnesium-nickel-iron-containing light stabilizer product.

Example 2

The salts of soluble divalent and trivalent metal cations used are magnesium nitrate hexahydrate (Mg(NO ₃ ) ₂ 6H ₂ O), nickel nitrate hexahydrate (Ni(NO ₃ ) ₂ 6H ₂ O) and nitric acid nonahydrate Aluminum (Al(NO ₃ ) ₃ .9H ₂ O).

Weigh 5.77g of magnesium nitrate hexahydrate, 6.54g of nickel nitrate hexahydrate and 12.66g of aluminum nitrate nonahydrate into a 200mL beaker, add 150mL of secondary water, and stir to dissolve them completely.

Weigh 6.08g of urea (H ₂ NCONH ₂ ), add it into the salt solution, transfer it to a hydrothermal reaction kettle after being completely dissolved, and react at 160°C for 4h.

After taking it out, cool it naturally, filter, wash, dry in a constant temperature blast drying oven at 80°C for 8 hours, grind, and sieve to obtain a magnesium-nickel-iron-containing light stabilizer product.

Example 3

The salts of soluble divalent and trivalent metal cations used are magnesium nitrate hexahydrate (Mg(NO ₃ ) ₂ 6H ₂ O), nickel nitrate hexahydrate (Ni(NO ₃ ) ₂ 6H ₂ O) and nitric acid nonahydrate Aluminum (Al(NO ₃ ) ₃ .9H ₂ O).

Weigh 4.51g of magnesium nitrate hexahydrate, 2.60g of nickel nitrate hexahydrate and 3.39g of aluminum nitrate nonahydrate into a 200mL beaker, add 150mL of secondary water, and stir to dissolve them completely.

Weigh 2.16g of urea (H ₂ NCONH ₂ ), add it into the salt solution, transfer it to a hydrothermal reaction kettle after being completely dissolved, and react at 100°C for 48h.

After taking it out, cool it naturally, filter, wash, dry in a constant temperature blast drying oven at 80°C for 8 hours, grind, and sieve to obtain a magnesium-nickel-iron-containing light stabilizer product.

Example 4

The salts of soluble divalent and trivalent metal cations used are magnesium nitrate hexahydrate (Mg(NO ₃ ) ₂ 6H ₂ O), nickel nitrate hexahydrate (Ni(NO ₃ ) ₂ 6H ₂ O) and nitric acid nonahydrate Aluminum (Al(NO ₃ ) ₃ .9H ₂ O).

Weigh 11.53g of magnesium nitrate hexahydrate, 6.54g of nickel nitrate hexahydrate and 8.43g of aluminum nitrate nonahydrate into a 200mL beaker, add 150mL of secondary water, and stir to dissolve them completely.

Weigh 10.13g of urea (H ₂ NCONH ₂ ), add it into the salt solution, transfer it to a hydrothermal reaction kettle after being completely dissolved, and react at 120°C for 12h.

After taking it out, cool it naturally, filter, wash, dry in a constant temperature blast drying oven at 80°C for 8 hours, grind, and sieve to obtain a magnesium-nickel-iron-containing light stabilizer product.

The light stabilizer obtained above is added to polypropylene, and after kneading at 180°C, a light-aging-resistant polypropylene composite material is obtained. Among them, the addition amount of light stabilizer in the corresponding light-aging polypropylene composite material is 1%, 2%, 4%, 6% respectively; The relationship was compared, and at the same time, the polypropylene material obtained without adding a light stabilizer was used as a comparative example for comparison; the comparison results are shown in Figure 6. It can be seen from Figure 6 that adding the light stabilizer can significantly improve the light aging resistance of polypropylene.

Claims (7)

1. a kind of preparation method of light stabilizer, it is characterised in that the general formula of the light stabilizer is expressed as [M (II)_1-xM(Ⅲ)_x (OH)₂]^x+A_x/n ^n-·mH₂O, wherein, M (II) is bivalent metal ion Mg²⁺And Ni²⁺；M (III) is trivalent metal ion Al³⁺；A It is the anion that valence state is-n valencys；X is the molar ratio of M (III) and [M (III)+M (II)]；M is to be hydrated water number, x=0.1~0.5, A is OH^-、CO₃ ^2-, m=0~10；The preparation method comprises the following steps：

A, it is the soluble-salt of divalence magnesium ion, bivalent nickel ion and trivalent aluminium ion is soluble in water, it is small to be made into cation concn In the salting liquid of 1.0mol/L, wherein bivalent cation mole is more than the 60% of total cation mole；

B, urea is added in this salting liquid and obtains mixed solution, the wherein molar concentration of urea is divalent metal mole 0.5~3.0 times of concentration；

C, this mixed solution is transferred in reaction kettle, is cooled to room temperature after hydro-thermal reaction 0.5h~48h, filtered, washing, The product drying after washing up to light stabilizer described in right 1.

2. preparation method according to claim 1, it is characterised in that the step A middle-jiao yang, function of the spleen and stomach ion concentration ranges are 0.1mol/L~1.0mol/L.

3. preparation method according to claim 1, it is characterised in that cation mole is more than total sun in the step A The 80% of ion mole.

4. preparation method according to claim 1, it is characterised in that the molar concentration of urea is divalence in the step B 1.0~2.0 times of metal cation molar concentration.

5. preparation method according to claim 1, it is characterised in that the hydrothermal temperature of the step C for 100 DEG C~ 200℃。

6. preparation method according to claim 1, it is characterised in that the step C drying conditions are dry for 80 DEG C~120 DEG C Dry 4h~12h.

7. a kind of light aging resisting PP composite material, it is characterised in that by any preparation method systems of claim 1-6 The light stabilizer obtained is added in polypropylene, up to light aging resisting PP composite material after mixing, wherein, described fast light In aging PP composite material, the mass fraction of the light stabilizer is 0.05%~10%.