CN102504103A - Micro-crosslinked polydimethyl diallyl ammonium chloride (PDMDAAC) modified color fixing agent and synthetic method thereof - Google Patents
Micro-crosslinked polydimethyl diallyl ammonium chloride (PDMDAAC) modified color fixing agent and synthetic method thereof Download PDFInfo
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 97
- 238000010189 synthetic method Methods 0.000 title claims 3
- PZNOBXVHZYGUEX-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine;hydrochloride Chemical compound Cl.C=CCNCC=C PZNOBXVHZYGUEX-UHFFFAOYSA-N 0.000 title 1
- 239000000178 monomer Substances 0.000 claims abstract description 86
- 238000004132 cross linking Methods 0.000 claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 7
- 238000001308 synthesis method Methods 0.000 claims abstract 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 48
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 48
- 239000003999 initiator Substances 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 26
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 10
- 235000019270 ammonium chloride Nutrition 0.000 claims 5
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims 2
- 230000032683 aging Effects 0.000 claims 2
- 238000010438 heat treatment Methods 0.000 claims 2
- WGESLFUSXZBFQF-UHFFFAOYSA-N n-methyl-n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCN(C)CC=C WGESLFUSXZBFQF-UHFFFAOYSA-N 0.000 claims 2
- 230000037396 body weight Effects 0.000 claims 1
- GQOKIYDTHHZSCJ-UHFFFAOYSA-M dimethyl-bis(prop-2-enyl)azanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC=C GQOKIYDTHHZSCJ-UHFFFAOYSA-M 0.000 abstract description 8
- 229920000289 Polyquaternium Polymers 0.000 abstract description 6
- 238000004043 dyeing Methods 0.000 abstract description 3
- -1 triene Propyl methyl ammonium chloride Chemical class 0.000 abstract description 3
- 230000007812 deficiency Effects 0.000 abstract description 2
- 238000007639 printing Methods 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract 1
- 230000004048 modification Effects 0.000 description 41
- 238000012986 modification Methods 0.000 description 41
- 239000000975 dye Substances 0.000 description 17
- 229920000742 Cotton Polymers 0.000 description 13
- 238000007334 copolymerization reaction Methods 0.000 description 10
- 239000004744 fabric Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 238000013461 design Methods 0.000 description 8
- 238000010792 warming Methods 0.000 description 7
- 241000322338 Loeseliastrum Species 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 238000010186 staining Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005304 joining Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005562 fading Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
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- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- AJXBTRZGLDTSST-UHFFFAOYSA-N amino 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ON AJXBTRZGLDTSST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
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- 230000001276 controlling effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
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- 230000036541 health Effects 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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- DYUWTXWIYMHBQS-UHFFFAOYSA-N n-prop-2-enylprop-2-en-1-amine Chemical compound C=CCNCC=C DYUWTXWIYMHBQS-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
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- 238000011160 research Methods 0.000 description 1
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- 239000000984 vat dye Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
本发明涉及一种微交联型聚二甲基二烯丙基氯化铵改性固色剂及其合成方法,针对PDMDAAC固色剂目前存在的不足或弱点，将交联性单体三烯丙基甲基氯化铵（TAMAC）与单体二甲基二烯丙基氯化铵（DMDAAC）共聚，并通过控制产物的结构特点及相对分子质量（特征粘度）大小，从而获得了一种相对分子质量及结构均受控的微交联共聚改性PDMDAAC固色剂及其合成方法，为印染工业领域提供一类使干摩擦牢度及湿摩擦牢度均得到提高的新型聚季铵盐高技术新固色剂产品，本发明固色剂产品具有以下特点：特定的特征粘度值范围（0.10-1.00dL/g）、良好的固色性能；其结构中交联性结构单元TAMAC与基准结构单元DMDAAC的摩尔含量比有效控制在1/99~5/95。
The invention relates to a micro-crosslinked polydimethyldiallylammonium chloride modified color fixing agent and a synthesis method thereof. Aiming at the current deficiency or weakness of the PDMDAAC color fixing agent, the crosslinking monomer triene Propyl methyl ammonium chloride (TAMAC) is copolymerized with monomer dimethyl diallyl ammonium chloride (DMDAAC), and by controlling the structural characteristics and relative molecular mass (intrinsic viscosity) of the product, a kind of The micro-crosslinked copolymerized modified PDMDAAC color fixing agent with controlled relative molecular weight and structure and its synthesis method provide a new type of polyquaternium salt with improved dry rubbing fastness and wet rubbing fastness for the printing and dyeing industry. High-tech new color fixing agent product, the color fixing agent product of the present invention has the following characteristics: specific characteristic viscosity value range (0.10-1.00dL/g), good color fixing performance; in its structure, the crosslinking structural unit TAMAC and the benchmark The molar content ratio of the structural unit DMDAAC is effectively controlled at 1/99~5/95.
Description
Technical field
The present invention relates to a kind of laking agent and compound method thereof, particularly a kind of micro-cross-linked Poly Dimethyl Diallyl Ammonium Chloride modification laking agent and compound method thereof.
Background technology
Cotton fibre is as one of fabric fibre of the plain structure of a fibrid, because of himself has good moisture absorption type, heat retention and soft hand feeling aspect taking, and advantages such as cleaning and health care and degradable recycling, and favored by people; Simultaneously, people have the needs of different color to the clothing fabric in the life, will dye to fabric thus.The dyestuff that is used for cotton fiber dyeing mainly contains vat dyes, substantive dyestuff, thioxine dyes and reactive dyestuffs etc., but dyestuff and interfibrous reactive force are more weak and the not high factor of utilization ratio causes the dyefastness of dyestuff not ideal enough, needs to carry out fixation with laking agent.
Poly Dimethyl Diallyl Ammonium Chloride (PDMDAAC) laking agent is as one type of ideal quaternary ammonium salt polycation type aldehyde-free colour stabilizer comparatively; Because its molecular chain modular construction possibly have intermolecular forces effect comparatively closely with the similar characteristics of cotton fibre cellulosic structure; Cause it and on cotton fibre, should have good fixing property, can be applicable to the fixation of various dyestuffs on the cotton fibre.PDMDAAC fixation mechanism is to combine with ionic linkage through quaternary ammonium salt cationic in the structure and negatively charged ion in the dye structure to form the color lake to reach the fixation purpose; Be damaged easily but act on because of the ionic linkage effect of itself and dyestuff and with the interfibrous Van der Waals force of cotton fabric under the effect of external force such as friction, especially fastness to wet rubbing is still not ideal enough to cause crockfastness.Document 1 has been studied the fixing property of a series of micro-cross-linked cationic laking agent (its structure is a diallyl by hydrochloride and the triallyl multipolymer by hydrochloride); Research shows; Through linear structure the becoming type planar reticulated structure of little crosslinked mode with polycation type laking agent; Then can enlarge the reach between dyestuff and laking agent; Thereby help further improving its fixing property, but do not relate to little crosslinkedization modification problem of the cationic laking agent PDMDAAC of polyquaternium at present commonly used, also do not relate to critical problem [the Iwata M to its performance impact such as its structure control and relative molecular mass (intrinsic viscosity) control simultaneously; Saka T; Ikeda T, and Kondo N. Production of di-and tri allylamine copolymer [P]. JP 61 130 317,1986-06-18]; Simultaneously; Document 2 also shows; As one of them of resin type laking agent; The fixing property of PDMDAAC laking agent and its relative molecular mass (intrinsic viscosity) size have confidential relation; And the PDMDAAC laking agent of (0.24 ~ 0.47 dL/g) can show comparatively outstanding fixing property in the special characteristic viscosity magnitude range; But do not relate in the literary composition problems such as its little crosslinking structure modification [Yu Y K, Zhang Y J. Molecular-weight-controlled Synthesis and dye-fixing properties of poly (dimethyldiallylammonium chloride) [J]. Journal of Vinyl and Additive Technology, 2,010 16 (4): 277 ~ 283].
Summary of the invention
The objective of the invention is to present these deficiencies or the weakness that exists of PDMDAAC laking agent; Further design is with cross-linkable monomer triallyl ammonio methacrylate (TAMAC) and monomer diallyldimethylammonChloride Chloride (DMDAAC) copolymerization; And through controlling the constructional feature and relative molecular mass (intrinsic viscosity) size of product; Thereby a kind of relative molecular mass and structure all controlled little copolymerzation with cross-linking modification PDMDAAC laking agent and compound method thereof have been obtained; For the printing and dyeing industry field provides one type of new laking agent product of novel polyquaternium hi-tech that dry fastness and fastness to wet rubbing all are improved, its reaction equation suc as formula shown in.
Ultimate principle of the present invention is according to being:
On the one hand, with regard to molecular structure, in little crosslinked its structure of PDMDAAC modification by copolymerization laking agent of gained possible crosslinking degree promptly wherein the molar content of cross-linkable monomer unit (TAMAC) be the key factor that influences its fixing property.Cross when low when its degree of crosslinking, the reach between dyestuff and laking agent is abundant inadequately, and this moment, its fixing property was relatively poor; And its degree of crosslinking is when too high; May destroy that modification laking agent agent structure PDMDAAC itself has with cotton fibre similarity structurally; Thereby the tight effect that influences between laking agent and cotton fabric is to each other got in touch; Simultaneously its degree of crosslinking crosses that roughly its spatial volume is excessive makes that also gained modification laking agent is difficult to penetrate into fibrous inside and dyestuff fully acts on, and thus its fixing property is also formed negative impact.Therefore, cross-linkable monomer unit (TAMAC) content in its structure within the specific limits the time its fixing property better.On the other hand; Experimental study is found; Resin type laking agent with certain intrinsic viscosity value can show outstanding fixing property; Simultaneously, consider PDMDAAC modification by copolymerization laking agent as one of resin type laking agent, its relative molecular mass (in intrinsic viscosity) estimates to have close related with its fixing property.When relative molecular mass is too small, the reactive force of itself and dyestuff a little less than, colour fixation is relatively poor; And relative molecular mass then forms gel or deposition easily and is difficult to penetrate into fibrous inside and the dyestuff effect when excessive.Therefore, can influence its colour fixation; Thereby control considers that PDMDAAC modification by copolymerization laking agent relative molecular mass then can improve its colour fixation within the specific limits.
In synthetic preparation process, the structure control of the little crosslinked PDMDAAC modification by copolymerization laking agent of gained can realize through the molar ratio of cross-linkable monomer (TAMAC) in the telo merization process and benchmark monomer (DMDAAC).Simultaneously; Its relative molecular mass control can realize according to following theory: for radical polymerization; The kinetic chain length of its resulting polymers is directly proportional with monomer concentration; With the square root of initiator concentration (initiator amount) be inverse ratio [Pan Zuren. polymer chemistry (third edition) [M]. Beijing: Chemical Industry Press, 2003:43,44]; The polymer kinetics chain length is big more, and the polymerization degree is just big more, and its relative molecular mass is just big more.Therefore, can be through regulating the relative molecular mass size that monomer concentration (initial monomer massfraction) and initiator concentration processing condition such as (initiator amounts) are controlled resulting polymers.The present invention comes effectively with this principle design through factors such as Collaborative Control reaction monomers concentration (initial monomer massfraction) and initiator amounts, and the relative molecular mass size of control gained laking agent is in the special characteristic range of viscosities; The molar ratio of cross-linkable monomer (TAMAC) and benchmark monomer (DMDAAC) is realized its structure control in the telo merization process simultaneously, to obtain corresponding micro-cross-linked PDMDAAC modification laking agent product.
Realize that technical solution of the present invention is:
According to the principle foundation, design following implementation step:
Step 1, cross-linkable monomer TAMAC and the benchmark monomer DMDAAC that gets metering joins in the reactor drum and is made into initial monomer solution;
Step 2 is filled nitrogen in reactor drum, join in the constant pressure funnel after initiator ammonium persulfate APS is made into dilute solution;
Step 3 heats up, and stirs evenly to drip initiator ammonium persulfate APS dilute solution down, drips off the back and keeps temperature to continue reaction;
Step 4, heat up back and slaking obtain the little crosslinked PDMDAAC modification laking agent of title product.
TAMAC monomer described in the step 1 and the monomeric mol ratio of DMDAAC are m
(TAMAC)/ n
(DMDAAC)=1/99 ~ 5/95, described initial monomer liquid quality fraction is 35%-50%;
Described cross-linkable monomer TAMAC processes through following method: being solvent with acetone, is that methyl NSC 20948 and the propenyl chloride of 1:1 reacts 24 h and make in about 30 ℃ with mol ratio.
Initiator ammonium persulfate APS described in the step 2 is the 4%-11% of total monomer quality (TAMAC and DMDAAC quality summation), and described initiator ammonium persulfate APS dilute solution concentration is 0.1-0.3g/ml.
Temperature of reaction described in the step 3 is 60-70 ℃, and the described dropping time is 2.0-3.0 h, and the described reaction times is 3.0-4.0 h.
Temperature of reaction described in the step 4 is 75-85 ℃; The described curing time is more than the 2h; Described little crosslinked PDMDAAC modification laking agent intrinsic viscosity value is 0.10-1.00 dL/g, and bridging property structural unit TAMAC is 1/99 ~ 5/95 with the molar content ratio of benchmark architecture cells D MDAAC in the structure.
Compared with prior art, laking agent product of the present invention has following characteristics:
(1) products obtained therefrom has specific intrinsic viscosity value scope (0.10-1.00 dL/g), has good fixing property;
(2) molar content of bridging property structural unit TAMAC and benchmark architecture cells D MDAAC is controlled at 1/99 ~ 5/95 than effectively in its structure;
(3) its metal to-metal contact of product can reach more than 4 grades, and fastness such as its wet friction preferably can reach 4 grades, are superior to 0.5 ~ 1.0 grade of domestic and international commercial like product, and its preparation technology and fixing property all have satisfactory stability property, and application prospect is better;
(4) the micro-cross-linked PDMDAAC modification laking agent of gained of the present invention can directly use, and its method of use is identical with the method for use of existing polyquaternium laking agent, is convenient to its wide popularization and application.
Description of drawings
Fig. 1 is the micro-cross-linked PDMDAAC modification of a present invention laking agent synthetic process flow sheet.
Fig. 2 is the infared spectrum of the micro-cross-linked PDMDAAC modification of the present invention laking agent.
Fig. 3 is the nuclear magnetic resonance map of the micro-cross-linked PDMDAAC modification of the present invention laking agent.
Embodiment
Come the present invention is described further through embodiment below, purpose is better to understand content of the present invention.But the example of being lifted does not limit protection scope of the present invention.
Micro-cross-linked Poly Dimethyl Diallyl Ammonium Chloride modification laking agent compound method is carried out according to the following steps:
The first step, (two kinds of monomeric mol ratios are m to get cross-linkable monomer TAMAC and the industrial DMDAAC monomer of metering
(TAMAC)/ n
(DMDAAC)=1/99 ~ 5/95) joins in the reactor drum and be made into the initial monomer solution that massfraction is 35%-50%;
Second step, in reactor drum, fill nitrogen, take by weighing and account for total monomer quality (TAMAC and DMDAAC quality summation) and join in the constant pressure funnel for the initiator ammonium persulfate APS of 4%-11% and after being made into the dilute solution of 0.1-0.3g/ml;
The 3rd step was warming up to 60-70 ℃, stirred evenly to drip initiator ammonium persulfate APS dilute solution down, and the dropping time is 2.0-3.0 h, and initiator solution drips off the back and keeps 60-70 ℃ of temperature to continue reaction 3.0-4.0 h;
The 4th step was warming up to 75-85 ℃ and more than slaking 2 h, obtained title product;
In the 5th step, measures above-mentioned product feature viscosity number through slaking to represent its relative molecular mass big or small.
Cross-linkable monomer TAMAC in the first step prepares as follows: being solvent with acetone, is that methyl NSC 20948 and the propenyl chloride of 1:1 reacts 24 h and make in about 30 ℃ with mol ratio.
Embodiment 1
The present invention's design comes effectively through factors such as Collaborative Control reaction monomers concentration (initial monomer massfraction) and initiator amounts, and the relative molecular mass size of the micro-cross-linked PDMDAAC modification by copolymerization laking agent of control is in the special characteristic range of viscosities; The molar ratio of cross-linkable monomer (TAMAC) and benchmark monomer (DMDAAC) is realized its structure control in the telo merization process simultaneously; And obtain corresponding micro-cross-linked PDMDAAC modification laking agent product; Cross-linkable monomer TAMAC used among each embodiment makes as stated above, and concrete steps are following:
The first step, (two kinds of monomeric mol ratios are m to get cross-linkable monomer TAMAC and the industrial DMDAAC monomer of metering
(TAMAC)/ n
(DMDAAC)=1/99) joining in the reactor drum and being made into massfraction is 35% initial monomer solution;
Second step, open the nitrogen introducing valve door, to remove the air in the reaction flask, stop logical nitrogen behind 30 min than atm number;
The 3rd the step, take by weighing account for total monomer quality (TAMAC and DMDAAC quality summation) be 11% initiator ammonium persulfate APS and be made into the dilute solution that concentration is 0.1g/ml after join in the constant pressure funnel;
In the 4th step, solution temperature rises to 60 ℃, stirs evenly to drip initiator ammonium persulfate APS dilute solution down, and the dropping time is 2 h, and initiator solution drips off the back and keeps 60 ℃ of temperature to continue reaction 4 h;
The 5th step was warming up to 75 ℃ of slaking 2 h (further improve the monomer conversion of product, help improving the colour fixation of products obtained therefrom), obtained title product.
Measure its intrinsic viscosity size through the Ubbelohde viscometer method; Recording its intrinsic viscosity value is 0.10 dL/g, and bridging property structural unit TAMAC is 1/99 with the molar content ratio of benchmark architecture cells D MDAAC in the micro-cross-linked PDMDAAC modification of the title product laking agent structure.
Embodiment 2
The present invention's design comes effectively through factors such as Collaborative Control reaction monomers concentration (initial monomer massfraction) and initiator amounts, and the relative molecular mass size of the micro-cross-linked PDMDAAC modification by copolymerization laking agent of control is in the special characteristic range of viscosities; The molar ratio of cross-linkable monomer (TAMAC) and benchmark monomer (DMDAAC) is realized its structure control in the telo merization process simultaneously; And obtain corresponding micro-cross-linked PDMDAAC modification laking agent product, concrete steps are following:
The first step, (two kinds of monomeric mol ratios are m to get cross-linkable monomer TAMAC and the industrial DMDAAC monomer of metering
(TAMAC)/ n
(DMDAAC)=1/99) joining in the reactor drum and being made into massfraction is 50% initial monomer solution;
Second step, open the nitrogen introducing valve door, to remove the air in the reaction flask, stop logical nitrogen behind 30 min than atm number;
The 3rd the step, take by weighing account for total monomer quality (TAMAC and DMDAAC quality summation) be 5% initiator ammonium persulfate APS and be made into the dilute solution that concentration is 0.2g/ml after join in the constant pressure funnel;
In the 4th step, the reaction soln temperature rises to 70 ℃, stirs evenly to drip initiator ammonium persulfate APS dilute solution down, and the dropping time is 2 h, and initiator solution drips off the back and keeps 70 ℃ of temperature to continue reaction 4 h;
The 5th step was warming up to 85 ℃ of slaking 2h, obtained title product.
Measure its intrinsic viscosity size through the Ubbelohde viscometer method; Recording its intrinsic viscosity value is 0.52 dL/g, and bridging property structural unit TAMAC is 1/99 with the molar content ratio of benchmark architecture cells D MDAAC in the micro-cross-linked PDMDAAC modification of the title product laking agent structure.
Embodiment 3
The present invention's design comes effectively through factors such as Collaborative Control reaction monomers concentration (initial monomer massfraction) and initiator amounts, and the relative molecular mass size of the micro-cross-linked PDMDAAC modification by copolymerization laking agent of control is in the special characteristic range of viscosities; The molar ratio of cross-linkable monomer (TAMAC) and benchmark monomer (DMDAAC) is realized its structure control in the telo merization process simultaneously; And obtain corresponding micro-cross-linked PDMDAAC modification laking agent product, concrete steps are following:
The first step, (two kinds of monomeric mol ratios are m to get cross-linkable monomer TAMAC and the industrial DMDAAC monomer of metering
(TAMAC)/ n
(DMDAAC)=3/97) joining in the reactor drum and being made into massfraction is 46% initial monomer solution;
Second step, open the nitrogen introducing valve door, to remove the air in the reaction flask, stop logical nitrogen behind 30 min than atm number;
The 3rd the step, take by weighing account for total monomer quality (TAMAC and DMDAAC quality summation) be 4% initiator ammonium persulfate APS and be made into the dilute solution that concentration is 0.3g/ml after join in the constant pressure funnel;
In the 4th step, the reaction soln temperature rises to 60 ℃, stirs evenly to drip initiator ammonium persulfate APS dilute solution down, and the dropping time is 2 h, and initiator solution drips off the back and keeps 60 ℃ of temperature to continue reaction 4 h;
The 5th step was warming up to 85 ℃ of slaking 2 h, obtained title product.
Measure its intrinsic viscosity size through the Ubbelohde viscometer method, recording its intrinsic viscosity value is 1.00 dL/g, and bridging property structural unit TAMAC and the molar content of benchmark architecture cells D MDAAC are than 3/97 in the micro-cross-linked PDMDAAC modification of the title product laking agent structure.
Embodiment 4
The present invention's design comes effectively through factors such as Collaborative Control reaction monomers concentration (initial monomer massfraction) and initiator amounts, and the relative molecular mass size of the micro-cross-linked PDMDAAC modification by copolymerization laking agent of control is in the special characteristic range of viscosities; The molar ratio of cross-linkable monomer (TAMAC) and benchmark monomer (DMDAAC) is realized its structure control in the telo merization process simultaneously; And obtain corresponding micro-cross-linked PDMDAAC modification laking agent product, concrete steps are following:
The first step, (two kinds of monomeric mol ratios are m to get cross-linkable monomer TAMAC and the industrial DMDAAC monomer of metering
(TAMAC)/ n
(DMDAAC)=5/95) joining in the reactor drum and being made into massfraction is 37% initial monomer solution;
Second step, open the nitrogen introducing valve door, to remove the air in the reaction flask, stop logical nitrogen behind 30 min than atm number;
The 3rd the step, take by weighing account for total monomer quality (TAMAC and DMDAAC quality summation) be 10% initiator ammonium persulfate APS and be made into the dilute solution that concentration is 0.2g/ml after join in the constant pressure funnel;
In the 4th step, the reaction soln temperature rises to 60 ℃, stirs evenly to drip initiator ammonium persulfate APS dilute solution down, and the dropping time is 2.5h, and initiator solution drips off the back and keeps 60 ℃ of temperature to continue reaction 3.5 h;
The 5th step was warming up to 85 ℃ of slaking 4h, obtained title product.
Measure its intrinsic viscosity size through the Ubbelohde viscometer method, recording its intrinsic viscosity value is 0.18 dL/g, and bridging property structural unit TAMAC and the molar content of benchmark architecture cells D MDAAC are than 5/95 in the micro-cross-linked PDMDAAC modification of the title product laking agent structure.
Embodiment 5
The present invention's design comes effectively through factors such as Collaborative Control reaction monomers concentration (initial monomer massfraction) and initiator amounts, and the relative molecular mass size of the micro-cross-linked PDMDAAC modification by copolymerization laking agent of control is in the special characteristic range of viscosities; The molar ratio of cross-linkable monomer (TAMAC) and benchmark monomer (DMDAAC) is realized its structure control in the telo merization process simultaneously; And obtain corresponding micro-cross-linked PDMDAAC modification laking agent product, concrete steps are following:
The first step, (two kinds of monomeric mol ratios of monomer are m to get cross-linkable monomer TAMAC and the industrial DMDAAC of metering
(TAMAC)/ n
(DMDAAC)=5/95) joining in the reactor drum and being made into massfraction is 41% initial monomer solution;
Second step, open the nitrogen introducing valve door, to remove the air in the reaction flask, stop logical nitrogen behind 30 min than atm number;
The 3rd the step, take by weighing account for total monomer quality (TAMAC and DMDAAC quality summation) be 9% initiator ammonium persulfate APS and be made into the dilute solution that concentration is 0.2g/ml after join in the constant pressure funnel;
In the 4th step, the reaction soln temperature rises to 60 ℃, stirs evenly to drip initiator ammonium persulfate APS dilute solution down, and the dropping time is 3 h, and initiator solution drips off the back and keeps 60 ℃ of temperature to continue reaction 3 h;
The 5th step was warming up to 85 ℃ of slaking 2 h, obtained title product.
Measure its intrinsic viscosity size through the Ubbelohde viscometer method; Recording its intrinsic viscosity value is 0.65 dL/g; Bridging property structural unit TAMAC and the molar content of benchmark architecture cells D MDAAC are than 5/95 in the micro-cross-linked PDMDAAC modification of the title product laking agent structure; Through ir spectra and nucleus magnetic resonance its structure is characterized, the result is shown in Fig. 2 and 3.
Application examples
According to related method among GB GB/T 3920-2008 and the GB GB/T 3921-2008, the micro-cross-linked PDMDAAC modification laking agent of mensuration and more different relative molecular mass size and constructional feature is to the fixing property of various dyestuffs on the cotton fabric (reactive scarlet 3BS and reactive brilliant bule KNR etc.).
Comparative Examples 1
The micro-cross-linked PDMDAAC modification laking agent of different relative molecular mass sizes and constructional feature is listed in table 1 to the colour fixation of reactive scarlet 3BS dyestuff on the cotton fabric.Wherein product is No. 1, No. 8, No. 16; Be respectively synthetic the obtaining of condition of embodiment 1 ~ 5 for No. 17 and No. 21; Laking agent LYPF is the commercially available PDMDAAC laking agent product that Shandong chemical industry ltd provides; Laking agent PDAC is the commercially available PDMDAAC laking agent product that Jiangsu chemical industry ltd provides, and laking agent Fix is certain external BA-SF company cationic fixing agent, and blank value is each dyestuff colour fastness value of (before the fixation) during fixation not.
Its dry fastness of the micro-cross-linked PDMDAAC modification of gained laking agent all reaches 4 grades, and fastness to wet rubbing all can reach more than 3 grades, and calico staining all reaches the 4-5 level, and former state is faded and all reached the 4-5 level; It is better that wherein intrinsic viscosity scope cross-linkable monomer unit (TAMAC) molar content in 0.16-0.30 dL/g and structure thereof is controlled at 1% o'clock its fixing property; Its fixing property to dyestuffs such as reactive scarlet 3BS on the cotton fabric is: dry fastness reaches 4 grades respectively; Fastness to wet rubbing preferably all can reach 4 grades; Calico staining all reaches the 4-5 level; Former state is faded and is all reached the 4-5 level, obviously is superior to homemade unmodified PDMDAAC laking agent and external similar cationic laking agent (laking agent Fix) commonly used; Before and after the fixation, its dry fastness, soap calico staining and the former state fastness of fading can improve 0.5 grade, and its fastness to wet rubbing can improve 1 grade, thereby it should have a good application prospect as new class polyquaternium modification laking agent.
Comparative Examples 2
The micro-cross-linked PDMDAAC modification laking agent of different relative molecular mass sizes and constructional feature is listed in table 2 to the colour fixation of reactive brilliant bule KNR dyestuff on the cotton fabric.Wherein product is No. 1, No. 8 No. 16; Be respectively synthetic the obtaining of condition of embodiment 1 ~ 5 for No. 17 and No. 21; Laking agent LYPF is the commercially available PDMDAAC laking agent product that Shandong chemical industry ltd provides; Laking agent PDAC is the commercially available PDMDAAC laking agent product that Jiangsu chemical industry ltd provides, and laking agent Fix is certain external BA-SF company cationic fixing agent, and blank value is each dyestuff colour fastness value of (before the fixation) during fixation not.
The micro-cross-linked PDMDAAC modification of gained laking agent dry fastness all reaches the 4-5 level; Fastness to wet rubbing all can reach more than 3 ~ 4 grades; Calico staining all reaches the 4-5 level; Former state is faded and is all reached the 4-5 level, and it is better that wherein intrinsic viscosity scope cross-linkable monomer unit (TAMAC) molar content in 0.16-0.30 dL/g and structure thereof is controlled at 1% o'clock its fixing property, and its fixing property to dyestuffs such as reactive brilliant bule KNR on the cotton fabric is: dry fastness reaches the 4-5 level respectively; Fastness to wet rubbing preferably all can reach 4 grades; Calico staining all reaches the 4-5 level, and former state is faded and all reached the 4-5 level, obviously is superior to homemade unmodified PDMDAAC laking agent and similar cationic laking agent (laking agent Fix) commonly used; Before and after the fixation, its dry fastness, soap calico staining and the former state fastness integral body of fading can improve 0.5 grade, and its fastness to wet rubbing can improve 1 grade, thereby it should have a good application prospect as new class polyquaternium modification laking agent.
Claims (10)
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