CN102504102A - 3-hydroxyazetidine reactive group-containing poly dimethyl diallyl ammonium chloride modified colouring stabilizer and synthesis method thereof - Google Patents
3-hydroxyazetidine reactive group-containing poly dimethyl diallyl ammonium chloride modified colouring stabilizer and synthesis method thereof Download PDFInfo
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Abstract
The present invention relates to a 3-hydroxyazetidine reactive group-containing poly dimethyl diallyl ammonium chloride modified colouring stabilizer and a synthesis method thereof. According to the present invention, based on the weakness of the existing PDMDAAC modified colouring stabilizer in the prior art, a reactive monomer N,N-diallyl-3-hydroxyazetidine ammonium chloride (DHAC) and a reference monomer dimethyl diallyl ammonium chloride (DMDAAC) are subjected to a copolymerization reaction, and a molar ratio of the structural unit DHAC in the product to the DMDAAC and the relative molecular mass (intrinsic viscosity) of the product are controlled, such that the reactive group-containing PDMDAAC modified colouring stabilizer with the controllable relative molecular mass and the controllable structure and the synthesis method of the modified colouring stabilizer are obtained, and the new reactive polyquaternary ammonium salt high technology colouring stabilizer products are provided for the printing and dyeing industry, wherein the dry rubbing fastnesses and the wet rubbing fastnesses are improved through the new colouring stabilizer products. The 3-hydroxyazetidine reactive group-containing poly dimethyl diallyl ammonium chloride modified colouring stabilizer of the present invention has characteristics of particular intrinsic viscosity range of 0.10-1.00 dL/g and good colouring stabilizing property, and the molar ratio of the reactive structural unit DHAC to the reference structural unit DMDAAC in the structure is controlled to 1/99-20/80.
Description
Technical field
The present invention relates to cationic laking agent of a kind of reactive polyquaternium and compound method thereof, particularly a kind of 3-hydroxyl heterocyclic butane group reactive group Poly Dimethyl Diallyl Ammonium Chloride modification laking agent and compound method thereof of containing.
Background technology
Fabric fibre comprises natural fiber (cotton, numb, mao, thread etc.) and man-made fiber (regenerated fibre, synthon etc.); The enhancing of Along with people's environmental consciousness; The environment-friendly type natural fiber is just more and more favored, and in natural fiber, cotton fibre is because from have good moisture absorption type, heat retention and soft hand feeling in the wear behavior aspect; And cleaning and health care and degradable are recycled advantages such as performance, and on this piece wonderful stage of fabric fibre, are playing the part of important role; The main composition structure of cotton fibre is a Mierocrystalline cellulose.In order to satisfy the demand of people, thereby to dye to fabric to clothing fabric different colours.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; It is to get through radical polymerization with monomer diallyldimethylammonChloride Chloride (DMDAAC); Have structures such as five-ring, six-ring, be mainly five-membered ring structure.Its 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; Simultaneously because its molecular chain modular construction possibly have intermolecular forces effect comparatively closely with the similar characteristics of cotton fibre cellulosic structure; Thereby it should have good fixing property on cotton fibre, can be applicable on the cotton fibre directly, the fixation of dyestuffs such as sulfuration, phthalonitrile, azo and activity; 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.
The investigator notices above-mentioned situation both at home and abroad; Done research in various degree to the structurally-modified aspect of PDMDAAC laking agent; Form the reactive group of covalent linkage as in the PDMDAAC structure, introducing to react with group such as hydroxyl in dyestuff or the cotton fabric; Thereby the effect so that the form of covalent linkage is strengthened between PDMDAAC and cotton fibre or dyestuff is got in touch, and then can improve its color fixation fastness effectively; Concrete work as follows:
Document 1 [Daniher F A; Aspland J R. Wet fast dyed cellulosic materials [P]. US 4 735 628; 1988-4-5] carry out copolymerization with DMDAAC and N-methylol acryloyl, to certain substantive dyestuff fixation on the cotton fabric, the result shows with the PDMDAAC modification by copolymerization laking agent of gained; Washable calico staining fastness is increased to 4～5 grades greatly by 2～3 grades before and after the fixation; This possibly be because this laking agent structure in not only contain and dyestuff negatively charged ion effect bonded positively charged ion, but also contain can with the methylol structure of hydroxyl generation covalent cross-linking in the cotton fabric, cause its fastness to washing and increase.
Document 2 [Collins G W; Burkinshaw S M, Gordon R. Dyeing of textiles [P]. US 2001/0054209 A1,2001-12-27] allyl amine and DMADAAC are carried out copolymerization; When gained PDMDAAC modification by copolymerization laking agent is used for the cotton fabric fixation of certain reactive dyeing; The result shows, fade fastness and calico staining fastness of washable former state is increased to 5 grades (superlative degrees) by 3 grades before and after the fixation, because of the amino of nucleophilicity wherein can with not on the reactive chlorine of dying in the reactive dyestuffs effective covalent effect takes place; Thereby dye the water-soluble of reactive dyestuffs on having reduced not, cause it and show outstanding fixing property.
Document 3 [Yang Haitao, Zhou Xiangdong, Dong Juan etc. the synthetic and application [J] of AM-DMDAAC copolymerization laking agent. printing and dyeing; 2010, (5): 10-13,23.] acrylic amide and DMADAAC are carried out copolymerization; When gained PDMDAAC modification by copolymerization laking agent was used for the cotton fabric fixation of certain reactive dyeing, the result showed that its fastness to wet rubbing can reach 3 grades; Dry fastness can reach 4 grades, and the calico staining fastness of soaping can reach 4 grades.
Though all there is certain research the structurally-modified aspect to the PDMDAAC laking agent in the domestic and foreign literature, has following defective:
(1) weakness of related PDMDAAC modification by copolymerization laking agent is that harmful formaldehyde may decomposed and discharge to wherein N-methylol structure (deriving from the condenses of formaldehyde and amine) in dyeing and finishing process in the document 1, and feature of environmental protection security is not good enough; In addition, its fixing property aspect only relates to washable calico staining fastness, and the fastness problems of relatively paying close attention at present such as unlubricated friction scrape along wet friction is not studied, and the reference value that causes its present application performance is limited.
(2) document 2 its emphasis fade to corresponding PDMDAAC modification by copolymerization laking agent washable former state during dye fixing on cotton fabric respectively and fastness problem such as calico staining has been carried out comparatively systematic study; But the fastness problems of relatively paying close attention at present such as unlubricated friction scrape along wet friction are not studied, the reference value that causes its present application performance is limited.
(3) the document 3 fastness problems such as unlubricated friction scrape along wet friction of having studied one type of PDMDAAC modification by copolymerization laking agent are studied, but its fastness to wet rubbing is merely 3 grades; In addition, its fixing property does not especially carry out lateral comparison with unmodified PDMDAAC laking agent etc. with similar laking agent product yet, causes the superiority-inferiority that is difficult on this product application performance of objective evaluation.
(4) document 1,2, and 3 have all studied the synthetic of different PDMDAAC modification by copolymerization laking agent, but do not relate to the critical problem to its performance impact such as its structure control and relative molecular mass (intrinsic viscosity) control.
Summary of the invention
The present invention is directed to these weakness that PDMDAAC modification laking agent exists at present; Design is with reactive monomer N; N-diallyl-3-hydroxyl heterocyclic butane ammonium chloride (DHAC) and benchmark monomer diallyldimethylammonChloride Chloride (DMDAAC) copolymerization; And molar ratio and relative molecular mass (intrinsic viscosity) size thereof through structural unit DHAC and DMDAAC in the control product; Thereby obtained a kind of relative molecular mass and structure all controlled contain reactive group PDMDAAC modification laking agent and compound method (relative molecular mass and all controlled Poly Dimethyl Diallyl Ammonium Chloride (PDMDAAC) modification by copolymerization laking agent and the compound method thereof of structure that contain 3-hydroxyl heterocyclic butane group reactive group) thereof; For the printing and dyeing industry field provides one type of new laking agent product of reactive 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, reactive group (DHAC) molar content that gained contains in its structure of PDMDAAC modification by copolymerization laking agent of reactive group is the key factor that influences its fixing property.When reactive group content wherein was very few, it can not form with cotton fabric that abundant effectively covalent effect combines was that effect between laking agent and cotton fabric is abundant inadequately, and this moment, its fixing property increased not quite; And its reactive group content is when too much; May destroy that 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; Also its fixing property is formed negative impact, in addition, therefore the cost of gained laking agent product also possibly improve; Therefore, the reactive group content in its modification laking agent molecular structure within the specific limits the time its fixing property better.On the other hand; Document and experimental study are found; Resin type laking agent with certain intrinsic viscosity value can show outstanding fixing property; Because PDMDAAC modification by copolymerization laking agent is a kind of resin type laking agent, its relative molecular mass (in intrinsic viscosity) estimates 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 for penetrating into fibrous inside and the dyestuff effect, thereby can influence its colour fixation when excessive.Therefore, control 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 reactive PDMDAAC modification by copolymerization of gained laking agent can realize through the molar ratio of reactive monomer (DHAC) 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; The present invention is a foundation with this principle; 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 control gained laking agent is in the special characteristic range of viscosities; The molar ratio of reactive monomer (DHAC) and benchmark monomer (DMDAAC) is realized its structure control in the telo merization process simultaneously, to obtain containing reactive group PDMDAAC modification laking agent product accordingly.
The technical scheme that realizes the object of the invention is:
According to the principle foundation, design following implementation step:
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 title product and contain reactive group PDMDAAC modification laking agent.
DHAC monomer described in the step 1 and the monomeric mol ratio of DMDAAC are m
(DHAC)/ n
(DMDAAC)=1/99 ~ 20/80, described initial monomer liquid quality fraction is 40%-55%;
Described DHAC processes through following method: 1:1 takes by weighing NSC 20948 and epoxy chloropropane in molar ratio; And the deionized water of adding and the suitable volume of reaction raw materials (NSC 20948 and epoxy chloropropane); Earlier at 20 ~ 30 ℃ of reaction 4 h; Further be warming up to 80 ℃ of reaction 2 h then, can obtain the DHAC monomer solution.
Initiator ammonium persulfate APS described in the step 2 is the 1%-5% of total monomer quality (DHAC 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 55-65 ℃, 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 65-75 ℃; 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 reactive structural unit DHAC is 1/99 ~ 20/80 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) the reactive structural unit DHAC in its structure is controlled to be 1/99 ~ 20/80 with the molar content ratio of benchmark architecture cells D MDAAC;
(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 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 containing reactive group PDMDAAC modification laking agent and can directly use of gained of the present invention, and its method of use is similar with the method for use of existing similar laking agent, is convenient to its wide popularization and application.
Description of drawings
Fig. 1 is that the present invention contains reactive unit PDMDAAC modification laking agent synthetic process flow sheet.
Fig. 2 is the infrared spectrogram that the present invention contains reactive unit PDMDAAC modification laking agent among the embodiment 1.
Fig. 3 is the nucleus magnetic resonance figure that the present invention contains reactive unit PDMDAAC modification laking agent among the embodiment 1.
Embodiment
Come the present invention is described further through embodiment below, purpose is better to understand content of the present invention.The example of therefore, being lifted does not limit protection scope of the present invention.
Containing reactive group Poly Dimethyl Diallyl Ammonium Chloride modification laking agent compound method carries out according to the following steps:
The first step, (two kinds of monomeric mol ratios are m to get reactive monomer DHAC and the industrial DMDAAC monomer of metering
(DHAC)/ n
(DMDAAC)=1/99 ~ 20/80) joins in the reactor drum and be made into the initial monomer solution that massfraction is 40%-55%;
Second step, in reactor drum, fill nitrogen, take by weighing and account for total monomer quality (DHAC and DMDAAC quality summation) and join in the constant pressure funnel for the initiator ammonium persulfate APS of 1%-5% and after being made into the dilute solution of 0.1-0.3g/ml;
The 3rd step was warming up to 55-65 ℃, 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 55-65 ℃ of temperature to continue reaction 3.0-4.0 h;
The 4th step was warming up to 65-75 ℃ and more than slaking 2 h, obtained title product and contained reactive group PDMDAAC modification laking agent;
In the 5th step, measures above-mentioned product feature viscosity number through slaking to represent its relative molecular mass big or small.
The described DHAC of the first step processes through following method: 1:1 takes by weighing NSC 20948 and epoxy chloropropane in molar ratio; And the deionized water of adding and the suitable volume of reaction raw materials (NSC 20948 and epoxy chloropropane); Earlier at 20 ~ 30 ℃ of reaction 4 h; Further be warming up to 80 ℃ of reaction 2 h then, can obtain the DHAC monomer solution.
The relative molecular mass size that the present invention's design comes effectively control to contain reactive group PDMDAAC modification laking agent through factors such as Collaborative Control reaction monomers concentration (initial monomer massfraction) and initiator amounts is in the special characteristic range of viscosities; The molar ratio of reactive monomer (DHAC) and benchmark monomer (DMDAAC) is realized its structure control in the telo merization process simultaneously; And acquisition contains reactive group PDMDAAC modification laking agent product accordingly; DHAC used among each embodiment processes through aforesaid method, and concrete steps are following:
The first step, (two kinds of monomeric mol ratios are m to get reactive monomer DHAC and the industrial DMDAAC monomer of metering
(DHAC)/ n
(DMDAAC)=1/99) joining in the reactor drum and being made into the initial monomer liquid quality fraction is 40% reaction soln;
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;
In the 3rd step, join in the constant pressure funnel after taking by weighing the initiator ammonium persulfate APS that accounts for total monomer quality (DHAC and DMDAAC quality summation) 5% and being made into the dilute solution of 0.3g/ml;
In the 4th step, the reaction soln temperature rises to 55 ℃, stirs down and evenly drips initiator ammonium sulfate APS dilute solution, and the dropping time is 2 h, keeps 55 ℃ of temperature after initiator solution drips off and continues reaction 4 h;
The 5th step was warming up to 75 ℃ of slaking 2h, with the monomer conversion of further raising product, helped improving the colour fixation of products obtained therefrom, obtained title product and contained reactive group PDMDAAC modification laking agent.
Measure its intrinsic viscosity size through the Ubbelohde viscometer method; Recording its intrinsic viscosity value is 0.10 dL/g, and the molar content ratio that title product contains reactive structural unit DHAC and benchmark architecture cells D MDAAC in the reactive group PDMDAAC modification laking agent structure is 1/99.
Embodiment 2
The relative molecular mass size that the present invention's design comes effectively control to contain reactive group PDMDAAC modification laking agent through factors such as Collaborative Control reaction monomers concentration (initial monomer massfraction) and initiator amounts is in the special characteristic range of viscosities; The molar ratio of reactive monomer (DHAC) and benchmark monomer (DMDAAC) is realized its structure control in the telo merization process simultaneously; And obtain to contain reactive group PDMDAAC modification laking agent product accordingly, concrete steps are following:
The first step, (two kinds of monomeric mol ratios are m to get reactive monomer DHAC and the industrial DMDAAC monomer of metering
(DHAC)/ n
(DMDAAC)=5/95) joining in the reactor drum and being made into the initial monomer liquid quality fraction is 52.5% reaction soln;
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;
In the 3rd step, join in the constant pressure funnel after taking by weighing the initiator ammonium persulfate APS that accounts for total monomer quality (DHAC and DMDAAC quality summation) 3% and being made into the dilute solution of 0.2g/ml;
In the 4th step, the reaction soln temperature rises to 55 ℃, stirs evenly to drip initiator ammonium persulfate APS dilute solution down, and the dropping time is 3 h, keeps 55 ℃ of temperature after initiator solution drips off and continues reaction 3 h;
The 5th step was warming up to 65 ℃ of slaking 4 h, with the monomer conversion of further raising product, helped improving the colour fixation of products obtained therefrom, obtained title product and contained reactive group PDMDAAC modification laking agent.
Measure its intrinsic viscosity size through the Ubbelohde viscometer method; Recording its intrinsic viscosity value is 0.42 dL/g, and the molar content ratio that title product contains reactive structural unit DHAC and benchmark architecture cells D MDAAC in the reactive group PDMDAAC modification laking agent structure is 5/95.
Embodiment 3
The relative molecular mass size that the present invention's design comes effectively control to contain reactive group PDMDAAC modification laking agent through factors such as Collaborative Control reaction monomers concentration (initial monomer massfraction) and initiator amounts is in the special characteristic range of viscosities; The molar ratio of reactive monomer (DHAC) and benchmark monomer (DMDAAC) is realized its structure control in the telo merization process simultaneously; And obtain to contain reactive group PDMDAAC modification laking agent product accordingly, concrete steps are following:
The first step, (two kinds of monomeric mol ratios are m to get reactive monomer DHAC and the industrial DMDAAC monomer of metering
(DHAC)/ n
(DMDAAC)=9/91) joining in the reactor drum and being made into the initial monomer liquid quality fraction is 55% reaction soln;
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;
In the 3rd step, join in the constant pressure funnel after taking by weighing the initiator ammonium persulfate APS that accounts for total monomer quality (DHAC and DMDAAC quality summation) 2% and being made into the dilute solution of 0.2g/ml;
In the 4th step, the reaction soln temperature rises to 65 ℃, stirs down and evenly drips initiator ammonium sulfate APS dilute solution, and the dropping time is 2.5 h, keeps 65 ℃ of temperature after initiator solution drips off and continues reaction 3.5 h;
The 5th step was warming up to 75 ℃ of slaking 2 h, with the monomer conversion of further raising product, helped improving the colour fixation of products obtained therefrom, obtained title product and contained reactive group PDMDAAC modification laking agent.
Measure its intrinsic viscosity size through the Ubbelohde viscometer method; Recording its intrinsic viscosity value is 0.73 dL/g, and the molar content ratio that title product contains reactive structural unit DHAC and benchmark architecture cells D MDAAC in the reactive group PDMDAAC modification laking agent structure is 9/91.
Embodiment 4
The relative molecular mass size that the present invention's design comes effectively control to contain reactive group PDMDAAC modification laking agent through factors such as Collaborative Control reaction monomers concentration (initial monomer massfraction) and initiator amounts is in the specific viscosity scope; The molar ratio of reactive monomer (DHAC) and benchmark monomer (DMDAAC) is realized its structure control in the telo merization process simultaneously; And obtain to contain reactive group PDMDAAC modification laking agent product accordingly, concrete steps are following:
The first step, (two kinds of monomeric mol ratios are m to get reactive monomer DHAC and the industrial DMDAAC monomer of metering
(DHAC)/ n
(DMDAAC)=20/80) joining in the reactor drum and being made into the initial monomer liquid quality fraction is 55% reaction soln;
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;
In the 3rd step, join in the constant pressure funnel after taking by weighing the initiator ammonium persulfate APS that accounts for total monomer quality (DHAC and DMDAAC quality summation) 1% and being made into the dilute solution of 0.1g/ml;
In the 4th step, the reaction soln temperature rises to 65 ℃, stirs down and evenly drips initiator ammonium sulfate APS dilute solution, and the dropping time is 2 h, keeps 65 ℃ of temperature after initiator solution drips off and continues reaction 4 h;
The 5th step was warming up to 75 ℃ of slaking 2h, with the monomer conversion of further raising product, helped improving the colour fixation of products obtained therefrom, obtained title product and contained reactive group PDMDAAC modification laking agent.
Measure its intrinsic viscosity size through the Ubbelohde viscometer method; Recording its intrinsic viscosity value is 1.00 dL/g; The molar content ratio that title product contains reactive structural unit DHAC and benchmark architecture cells D MDAAC in the reactive group PDMDAAC modification laking agent structure is 20/80; 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 reactive group PDMDAAC modification laking agent that contains in different relative molecular masses (with intrinsic viscosity) size and constructional feature carries out fixation treatment to various dyestuffs on the cotton fabric (reactive scarlet 3BS and reactive brilliant bule KNR etc.); Afterwards the dyed cotton fabric after the fixation treatment is further baked about 3 min in 180 ℃; Cause the reactive group (3-hydroxyl heterocyclic butane group) in its structure effective covalent effect to take place and possibly further improve its fixing property, thereby obtain the fixing property that gained contains reactive group PDMDAAC modification laking agent with the cotton fabric hydroxyl with this.
Comparative Examples 1
The reactivity of different relative molecular mass sizes and constructional feature contains reactive group PDMDAAC modification laking agent the colour fixation of reactive scarlet 3BS dyestuff on the cotton fabric is listed in table 1.Wherein product is respectively synthetic the obtaining of condition among the embodiment 1 ~ 4 for No. 1, No. 16, No. 30 and No. 35; 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; 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.
Gained contains its dry fastness of reactive group PDMDAAC modification laking agent and all reaches more than 4 grades; Fastness to wet rubbing can reach more than 3 grades; Calico staining all reaches more than 4 grades; Former state is faded and is all reached more than 4 grades, and wherein the intrinsic viscosity scope is m at 0.20-0.47 dL/g and structure thereof with two kinds of structural unit molar content ratios
(DHAC)/ n
(DMDAAC)It is better to count 7/93 o'clock its fixing property; Its fixing property to dyestuffs such as reactive scarlet 3BS on the cotton fabric is: dry fastness reaches respectively more than 4 grades; 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 external similar famous product; Before and after the fixation, its dry fastness, soap calico staining and the former state fastness of fading can improve 0.5 grade ~ 1 grade, and its fastness to wet rubbing can improve 1 grade, thereby it should have a good application prospect as the reactive polyquaternium laking agent of new class.
Comparative Examples 2
The reactive group PDMDAAC modification laking agent that contains 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 respectively synthetic the obtaining of condition among the embodiment 1 ~ 4 for No. 1, No. 16, No. 30 and No. 35; 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; 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.
Gained contains its dry fastness of reactive group PDMDAAC modification laking agent and all reaches the 4-5 level; Fastness to wet rubbing all can reach more than the 3-4 level; Calico staining all reaches the 4-5 level; Former state is faded and is all reached the 4-5 level, and wherein the intrinsic viscosity scope is m at 0.20-0.47 dL/g and structure thereof with two kinds of structural unit molar content ratios
(DHAC)/ n
(DMDAAC)It is better to count 7/93 o'clock its fixing property; 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 external similar famous product; 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 the reactive polyquaternium laking agent of new class.
Claims (10)
1. one kind contains 3-hydroxyl heterocyclic butane group reactive group Poly Dimethyl Diallyl Ammonium Chloride modification laking agent, it is characterized in that said laking agent prepares according to the following steps:
Step 1 is got reactive monomer DHAC 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 title product and contain reactive group PDMDAAC modification laking agent.
2. by the described 3-hydroxyl heterocyclic butane group reactive group Poly Dimethyl Diallyl Ammonium Chloride modification laking agent that contains of claim 1; It is characterized in that DHAC monomer described in the step 1 and the monomeric mol ratio of DMDAAC are 1/99 ~ 20/80, described initial monomer liquid quality fraction is 40%-55%;
Described DHAC processes through following method: 1:1 takes by weighing NSC 20948 and epoxy chloropropane in molar ratio; And the deionized water of adding and the suitable volume of reaction raw materials; At 20 ~ 30 ℃ of reaction 4 h, further be warming up to 80 ℃ of reaction 2 h then earlier, can obtain the DHAC monomer solution.
3. by the described 3-hydroxyl heterocyclic butane group reactive group Poly Dimethyl Diallyl Ammonium Chloride modification laking agent that contains of claim 1; It is characterized in that the initiator ammonium persulfate APS described in the step 2 is the 1%-5% of total monomer quality, described initiator ammonium persulfate APS dilute solution concentration is 0.1-0.3g/ml.
4. by the described 3-hydroxyl heterocyclic butane group reactive group Poly Dimethyl Diallyl Ammonium Chloride modification laking agent that contains of claim 1; It is characterized in that the temperature of reaction described in the step 3 is 55-65 ℃; The described dropping time is 2-3h, and the described reaction times is 3-4h.
5. by the described 3-hydroxyl heterocyclic butane group reactive group Poly Dimethyl Diallyl Ammonium Chloride modification laking agent that contains of claim 1; It is characterized in that the temperature of reaction described in the step 4 is 65-75 ℃; Described curing time >=2h; Described product P DMDAAC modification laking agent intrinsic viscosity value is 0.10-1.00 dL/g, and reactive structural unit DHAC is 1/99 ~ 20/80 with the molar content ratio of benchmark architecture cells D MDAAC in the structure.
6. one kind contains 3-hydroxyl heterocyclic butane group reactive group Poly Dimethyl Diallyl Ammonium Chloride modification laking agent compound method, it is characterized in that said method carries out according to the following steps:
Step a gets reactive monomer DHAC 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 title product and contain reactive group PDMDAAC modification laking agent.
7. by the described 3-hydroxyl heterocyclic butane group reactive group Poly Dimethyl Diallyl Ammonium Chloride modification laking agent compound method that contains of claim 6; It is characterized in that DHAC monomer described in the step a and the monomeric mol ratio of DMDAAC are 1/99 ~ 20/80, described initial monomer liquid quality fraction is 40%-55%;
Described DHAC processes through following method: 1:1 takes by weighing NSC 20948 and epoxy chloropropane in molar ratio; And the deionized water of adding and the suitable volume of reaction raw materials; At 20 ~ 30 ℃ of reaction 4 h, further be warming up to 80 ℃ of reaction 2 h then earlier, can obtain the DHAC monomer solution.
8. by the described 3-hydroxyl heterocyclic butane group reactive group Poly Dimethyl Diallyl Ammonium Chloride modification laking agent compound method that contains of claim 6; It is characterized in that the initiator ammonium persulfate APS described in the step b is the 1%-5% of total monomer quality, described initiator ammonium persulfate APS dilute solution concentration is 0.1-0.3g/ml.
9. by the described 3-hydroxyl heterocyclic butane group reactive group Poly Dimethyl Diallyl Ammonium Chloride modification laking agent compound method that contains of claim 6; It is characterized in that the temperature of reaction described in the step c is 55-65 ℃; The described dropping time is 2-3h, and the described reaction times is 3-4h.
10. by the described 3-hydroxyl heterocyclic butane group reactive group Poly Dimethyl Diallyl Ammonium Chloride modification laking agent compound method that contains of claim 6, it is characterized in that the temperature of reaction described in the steps d is 65-75 ℃, described curing time >=2h.
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| CN103711011A (en) * | 2013-12-27 | 2014-04-09 | 福建清源科技有限公司 | Micro-crosslinking type poly(methacryloxyethyltrimethyl ammonium chloride) modified color fixing agent and preparation method thereof |
| CN103726369A (en) * | 2013-11-08 | 2014-04-16 | 绍兴鼎翔纺织品贸易有限公司 | Cationic fixing agent emulsion and preparation method thereof |
| CN106220785A (en) * | 2016-08-11 | 2016-12-14 | 四川省纺织科学研究院 | A kind of reactive polyquarternium-type is without the preparation method and application of aldehyde fixation crosslinking agent |
| CN110331605A (en) * | 2019-07-19 | 2019-10-15 | 绍兴中纺化工有限公司 | A kind of natural dye color fixing agent and preparation method thereof |
| CN111041862A (en) * | 2019-10-25 | 2020-04-21 | 深圳市迪威科技有限公司 | Method for modifying and dyeing all-cotton fabric |
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| CN103726369A (en) * | 2013-11-08 | 2014-04-16 | 绍兴鼎翔纺织品贸易有限公司 | Cationic fixing agent emulsion and preparation method thereof |
| CN103711011A (en) * | 2013-12-27 | 2014-04-09 | 福建清源科技有限公司 | Micro-crosslinking type poly(methacryloxyethyltrimethyl ammonium chloride) modified color fixing agent and preparation method thereof |
| CN103711011B (en) * | 2013-12-27 | 2015-07-01 | 福建清源科技有限公司 | Micro-crosslinking type poly(methacryloxyethyltrimethyl ammonium chloride) modified color fixing agent and preparation method thereof |
| CN106220785A (en) * | 2016-08-11 | 2016-12-14 | 四川省纺织科学研究院 | A kind of reactive polyquarternium-type is without the preparation method and application of aldehyde fixation crosslinking agent |
| CN110331605A (en) * | 2019-07-19 | 2019-10-15 | 绍兴中纺化工有限公司 | A kind of natural dye color fixing agent and preparation method thereof |
| CN110331605B (en) * | 2019-07-19 | 2021-10-08 | 绍兴中纺化工有限公司 | Natural dye color fixing agent and preparation method thereof |
| CN111041862A (en) * | 2019-10-25 | 2020-04-21 | 深圳市迪威科技有限公司 | Method for modifying and dyeing all-cotton fabric |
| CN114957546A (en) * | 2022-06-21 | 2022-08-30 | 南京理工大学 | Methyl aryl diallyl quaternary ammonium salt copolymer flocculant for treating reactive dye printing and dyeing wastewater |
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