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
- Publication number
- CN102504103A CN102504103A CN2011103709675A CN201110370967A CN102504103A CN 102504103 A CN102504103 A CN 102504103A CN 2011103709675 A CN2011103709675 A CN 2011103709675A CN 201110370967 A CN201110370967 A CN 201110370967A CN 102504103 A CN102504103 A CN 102504103A
- Authority
- CN
- China
- Prior art keywords
- cross
- micro
- laking agent
- monomer
- tamac
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a micro-crosslinked polydimethyl diallyl ammonium chloride (PDMDAAC) modified color fixing agent and a synthetic method thereof. Specific to the defects or disadvantages existing in the conventional PDMDAAC color fixing agent, a crosslinking monomer, i.e., triallyl methyl ammonium chloride (TAMAC) and monomer dimethyl diene propyl ammonium chloride (DMDAAC) are copolymerized, and the structural characteristics and the relative molecular mass (intrinsic viscosity) of a product are controlled, so that a micro-crosslinked copolymerization-modified PDMDAAC color fixing agent of which the relative molecular mass and structure are controlled is obtained, and a novel polyquatemary salt high-technology color fixing agent product which contributes to improving dry abrasive moisture and wet abrasive moisture is provided for the industrial field of dye printing. The color fixing agent product has the characteristics of specified intrinsic viscosity value range (0.10-1.00 dL/g) and high color fixing performance; and the molar content ratio of a cross-linking structural unit, i.e., TAMAC and a benchmark structural unit, i.e., DMDAAC is controlled effectively 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)
1. micro-cross-linked Poly Dimethyl Diallyl Ammonium Chloride modification laking agent is characterized in that said laking agent prepares according to the following steps:
Step 1 is got cross-linkable monomer TAMAC and benchmark monomer DMDAAC and is joined in the reactor drum and be 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.
2. micro-cross-linked Poly Dimethyl Diallyl Ammonium Chloride modification laking agent according to claim 1; It is characterized in that TAMAC monomer described in the step 1 and the monomeric mol ratio of DMDAAC are 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 makes in 30 ℃ of reaction 24 h with mol ratio.
3. micro-cross-linked Poly Dimethyl Diallyl Ammonium Chloride modification laking agent according to claim 1; It is characterized in that the initiator ammonium persulfate APS described in the step 2 is the 4%-11% of total monomer quality, described initiator ammonium persulfate APS dilute solution concentration is 0.1-0.3g/ml.
4. micro-cross-linked Poly Dimethyl Diallyl Ammonium Chloride modification laking agent according to claim 1 is characterized in that the temperature of reaction described in the step 3 is 60-70 ℃, and the described dropping time is 2-3 h, and the described reaction times is 3-4h.
5. micro-cross-linked Poly Dimethyl Diallyl Ammonium Chloride modification laking agent according to claim 1; It is characterized in that the temperature of reaction described in the step 4 is 75-85 ℃; Described curing time >=2h; The little crosslinked PDMDAAC modification laking agent intrinsic viscosity value of described product 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.
6. micro-cross-linked Poly Dimethyl Diallyl Ammonium Chloride modification laking agent compound method is characterized in that said method carries out according to the following steps:
Step a gets cross-linkable monomer TAMAC and benchmark monomer DMDAAC and joins in the reactor drum and be made into initial monomer solution;
Step b fills nitrogen in reactor drum, join in the constant pressure funnel after initiator ammonium persulfate APS is made into dilute solution;
Step c heats up, and stirs evenly to drip initiator ammonium persulfate APS dilute solution down, drips off the back and keeps temperature to continue reaction;
Steps d, heat up back and slaking obtain the little crosslinked PDMDAAC modification laking agent of title product.
7. micro-cross-linked Poly Dimethyl Diallyl Ammonium Chloride modification laking agent compound method according to claim 6; It is characterized in that TAMAC monomer described in the step a and the monomeric mol ratio of DMDAAC are 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 makes in 30 ℃ of reaction 24 h with mol ratio.
8. micro-cross-linked Poly Dimethyl Diallyl Ammonium Chloride modification laking agent compound method according to claim 6; It is characterized in that the initiator ammonium persulfate APS described in the step b is the 4%-11% of total monomer quality, described initiator ammonium persulfate APS dilute solution concentration is 0.1-0.3g/ml.
9. micro-cross-linked Poly Dimethyl Diallyl Ammonium Chloride modification laking agent compound method according to claim 6 is characterized in that the temperature of reaction described in the step c is 60-70 ℃, and the described dropping time is 2-3 h, and the described reaction times is 3-4 h.
10. micro-cross-linked Poly Dimethyl Diallyl Ammonium Chloride modification laking agent compound method according to claim 6 is characterized in that the temperature of reaction described in the steps d is 75-85 ℃, described curing time >=2h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103709675A CN102504103A (en) | 2011-11-21 | 2011-11-21 | Micro-crosslinked polydimethyl diallyl ammonium chloride (PDMDAAC) modified color fixing agent and synthetic method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103709675A CN102504103A (en) | 2011-11-21 | 2011-11-21 | Micro-crosslinked polydimethyl diallyl ammonium chloride (PDMDAAC) modified color fixing agent and synthetic method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102504103A true CN102504103A (en) | 2012-06-20 |
Family
ID=46216242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011103709675A Pending CN102504103A (en) | 2011-11-21 | 2011-11-21 | Micro-crosslinked polydimethyl diallyl ammonium chloride (PDMDAAC) modified color fixing agent and synthetic method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102504103A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103603217A (en) * | 2013-11-20 | 2014-02-26 | 上海德桑精细化工有限公司 | Color fixing agent and preparation method thereof |
| CN103724540A (en) * | 2013-11-08 | 2014-04-16 | 绍兴鼎翔纺织品贸易有限公司 | Fabric dye-fixing agent emulsion and preparation method thereof |
| CN103922944A (en) * | 2014-04-01 | 2014-07-16 | 浙江传化股份有限公司 | Cross-linkable quaternary ammonium salt water-soluble cationic monomer as well as preparation method and application thereof |
| CN105085441A (en) * | 2014-05-06 | 2015-11-25 | 中国石油化工股份有限公司 | Biquaternary ammonium salt compound and application thereof in solid-phase chemical cleaning agent |
| CN105780501A (en) * | 2016-05-10 | 2016-07-20 | 安徽天馨工艺制品集团有限公司 | Preparation method of high-moisture-permeability down feather with surface cross-linked silks |
| CN106319681A (en) * | 2016-08-29 | 2017-01-11 | 董晓 | Preparation method of easy-to-color anti-static spandex fibers |
| CN104892832B (en) * | 2013-12-27 | 2017-03-01 | 福建清源科技有限公司 | A kind of preparation method of micro-cross-linked polymethyl acyloxyethyl trimethyl ammonium chloride modification color fixing agent |
| CN105175631B (en) * | 2013-12-27 | 2017-08-25 | 石狮市清源精细化工有限公司 | A kind of preparation method of reactive dye cationic formaldehyde-free fixing agent |
| CN107893333A (en) * | 2017-11-21 | 2018-04-10 | 常州市阿曼特化工有限公司 | A kind of laundry care agent and preparation method thereof |
| CN108239223A (en) * | 2018-01-11 | 2018-07-03 | 中国科学院合肥物质科学研究院 | A kind of preparation method of the micro- crosslinked polydimethyl diallyl ammonium chloride of high relative molecular mass |
| CN110016103A (en) * | 2018-12-28 | 2019-07-16 | 福建清源科技有限公司 | A kind of modified hydroxymethyl starch polymer and its preparation method and application |
| CN110449138A (en) * | 2019-08-05 | 2019-11-15 | 江西师范大学 | A kind of preparation method of porous type polyquaternium gel adsorber |
| CN112376301A (en) * | 2020-11-16 | 2021-02-19 | 浙江大川新材料股份有限公司 | Formaldehyde-free color fixing agent and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0264710A1 (en) * | 1986-10-06 | 1988-04-27 | Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. | Water-soluble quaternary polyammonium salts, process for their preparation and their use |
| CN1282571A (en) * | 1999-06-29 | 2001-02-07 | Basf公司 | Use of crosslinked cation polymer in skin cosmetics and skin disease preparations |
| CN101186672A (en) * | 2006-11-15 | 2008-05-28 | 南京理工大学 | Water solution polymerization preparation method for dimethyl diallyl ammonium chloride and acrylamide copolymers |
| CN101891854A (en) * | 2010-07-05 | 2010-11-24 | 南京理工大学 | Relative molecular mass controlled polyquaternium color fixing agent and synthesizing method thereof |
-
2011
- 2011-11-21 CN CN2011103709675A patent/CN102504103A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0264710A1 (en) * | 1986-10-06 | 1988-04-27 | Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. | Water-soluble quaternary polyammonium salts, process for their preparation and their use |
| EP0264710B1 (en) * | 1986-10-06 | 1993-05-05 | Fraunhofer-Gesellschaft Zur Förderung Der Angewandten Forschung E.V. | Water-soluble quaternary polyammonium salts, process for their preparation and their use |
| CN1282571A (en) * | 1999-06-29 | 2001-02-07 | Basf公司 | Use of crosslinked cation polymer in skin cosmetics and skin disease preparations |
| CN101186672A (en) * | 2006-11-15 | 2008-05-28 | 南京理工大学 | Water solution polymerization preparation method for dimethyl diallyl ammonium chloride and acrylamide copolymers |
| CN101891854A (en) * | 2010-07-05 | 2010-11-24 | 南京理工大学 | Relative molecular mass controlled polyquaternium color fixing agent and synthesizing method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 贾旭 等: "聚二甲基二烯丙基氯化铵的控制聚合方法", 《石油化工》, vol. 37, no. 1, 31 December 2008 (2008-12-31), pages 49 - 54 * |
| 阎醒: "二甲基二烯丙基氯化铵的聚合与交联", 《油田化学》, vol. 9, no. 3, 30 September 1992 (1992-09-30), pages 259 - 261 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103724540A (en) * | 2013-11-08 | 2014-04-16 | 绍兴鼎翔纺织品贸易有限公司 | Fabric dye-fixing agent emulsion and preparation method thereof |
| CN103603217A (en) * | 2013-11-20 | 2014-02-26 | 上海德桑精细化工有限公司 | Color fixing agent and preparation method thereof |
| CN105175631B (en) * | 2013-12-27 | 2017-08-25 | 石狮市清源精细化工有限公司 | A kind of preparation method of reactive dye cationic formaldehyde-free fixing agent |
| CN104892832B (en) * | 2013-12-27 | 2017-03-01 | 福建清源科技有限公司 | A kind of preparation method of micro-cross-linked polymethyl acyloxyethyl trimethyl ammonium chloride modification color fixing agent |
| CN103922944A (en) * | 2014-04-01 | 2014-07-16 | 浙江传化股份有限公司 | Cross-linkable quaternary ammonium salt water-soluble cationic monomer as well as preparation method and application thereof |
| CN103922944B (en) * | 2014-04-01 | 2016-08-17 | 浙江传化股份有限公司 | A kind of crosslinkable quaternary ammonium salt water-soluble cationic monomer and its preparation method and application |
| CN105085441A (en) * | 2014-05-06 | 2015-11-25 | 中国石油化工股份有限公司 | Biquaternary ammonium salt compound and application thereof in solid-phase chemical cleaning agent |
| CN105780501A (en) * | 2016-05-10 | 2016-07-20 | 安徽天馨工艺制品集团有限公司 | Preparation method of high-moisture-permeability down feather with surface cross-linked silks |
| CN106319681A (en) * | 2016-08-29 | 2017-01-11 | 董晓 | Preparation method of easy-to-color anti-static spandex fibers |
| CN107893333A (en) * | 2017-11-21 | 2018-04-10 | 常州市阿曼特化工有限公司 | A kind of laundry care agent and preparation method thereof |
| CN108239223A (en) * | 2018-01-11 | 2018-07-03 | 中国科学院合肥物质科学研究院 | A kind of preparation method of the micro- crosslinked polydimethyl diallyl ammonium chloride of high relative molecular mass |
| CN110016103A (en) * | 2018-12-28 | 2019-07-16 | 福建清源科技有限公司 | A kind of modified hydroxymethyl starch polymer and its preparation method and application |
| CN110016103B (en) * | 2018-12-28 | 2021-08-31 | 福建清源科技有限公司 | Modified carboxymethyl starch polymer and preparation method and application thereof |
| CN110449138A (en) * | 2019-08-05 | 2019-11-15 | 江西师范大学 | A kind of preparation method of porous type polyquaternium gel adsorber |
| CN112376301A (en) * | 2020-11-16 | 2021-02-19 | 浙江大川新材料股份有限公司 | Formaldehyde-free color fixing agent and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102504103A (en) | Micro-crosslinked polydimethyl diallyl ammonium chloride (PDMDAAC) modified color fixing agent and synthetic method thereof | |
| CN101891854B (en) | Relative molecular mass controlled polyquaternium color fixing agent and synthesizing method thereof | |
| CN102797170B (en) | Formaldehyde-free fixing agent and preparation method thereof | |
| CN102504104A (en) | PDMDAAC modified color fixing agent containing 3-chlorine-2-hydroxyl propyl group reactive unit and synthesis method thereof | |
| CN101781857B (en) | Soap-free color-fixing agent emulsion and preparation method thereof | |
| CN100537891C (en) | A kind of preparation method of nano-level formaldehyde-free coating dyeing and printing adhesive agent and application | |
| CN103061148B (en) | Wet rubbing fastness improver for chitosan quaternary ammonium salt modified by organic silicon, and preparation method of improver | |
| CN102432772B (en) | Synthesis method of quaternized organosilicon modified acrylate emulsion | |
| CN102504102A (en) | 3-hydroxyazetidine reactive group-containing poly dimethyl diallyl ammonium chloride modified colouring stabilizer and synthesis method thereof | |
| CN102532399A (en) | Acrylic acid textile size and preparation method thereof | |
| CN103469614B (en) | Trilobal high-load cation dyeable modified polyester/cotton BLENDED FABRIC one-bath process method | |
| CN105566516B (en) | A kind of structure directing type composite initiator system and acrylamide polymer and its preparation method and application | |
| CN102977269B (en) | Chitosan acrylate graft latex and cotton fiber processing solution containing chitosan acrylate graft latex | |
| CN104892832A (en) | Preparation method of micro-crosslinked polymethacryloxyethyltrimethyl ammonium chloride modification fixing agent | |
| CN103936941A (en) | Amphiphilic core-shell emulsion adhesive for pigment printing of textile and preparation method thereof | |
| CN103232566B (en) | Preparation method of high-solid-content low-viscosity acrylate emulsion for sealing gum | |
| CN103113530A (en) | Preparation method of PVC (Polyvinyl Chloride) covalent bonding nanoparticle alloy resin | |
| CN1227318C (en) | Method for preparing formaldehyde-free coating adhesive for printing | |
| CN101492883A (en) | Macromolecule type wet friction fastness improver | |
| CN104610512A (en) | Preparation method of super-soft IPN (interpenetrating polymer network) pigment printing binder | |
| CN100393793C (en) | Polyvinyl chloride processing plasticizing modifier, its preparation method and application | |
| CN101942772A (en) | Low-formaldehyde soaping-resistant adhesive for textile pigment printing and preparation method thereof | |
| CN102108110A (en) | Method for preparing acrylate printing adhesive | |
| CN103897107A (en) | Method for preparing paper stiffness agent | |
| CN101735753B (en) | Acrylate emulsion adhesive with special structure and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120620 |