CN103161082A - Organosilicone modification pigment printing adhesion agent and preparation method thereof - Google Patents
Organosilicone modification pigment printing adhesion agent and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of high polymer chemistry and pigment printing adhesion agents, and particularly relates to an organosilicone modification pigment printing adhesion agent and a preparation method thereof. The organosilicone modification pigment printing adhesion agent is obtained through copolymerization between low molecular weight organosilicone emulsion and an unsaturated monomer, and the structure of an organosilicone modification macromolecular compound is shown as a general formula (I). The pigment printing adhesion agent has the superior application performances of being soft in hand feel, high in all fastnesses, convenient to apply and the like. Particularly, the pigment printing adhesion agent not only can be used as printing on pure cotton fabric, but also can be used as printing on pure chemical fiber or blended fabrics.
Description
Technical field
The invention belongs to polymer chemistry and pigment printing binding agent field, specifically a kind of research of silicone modified coating printing adhesive and preparation method thereof.
Background technology
COAT PRINTING is to utilize adhesive that pigment is adhered to printing method on textiles, is one of present most popular printing technique.Printing paste is comprised of colouring agent, adhesive, thickener and a small amount of auxiliary material, and the quality of printing adhesive is the principal element of restriction COAT PRINTING development.The printing adhesive of function admirable should consider print durability, fabric feeling and whether factor, particularly feel and the fastness of this three aspects: of network blocking.Now widely used adhesive is roughly three major types, i.e. esters of acrylic acid, butadiene type and polyurethanes.Wherein, acrylate adhesive epithelium transparency is high, is present the most frequently used adhesive; The butadiene type adhesive is soft, but easily yellowing, cost is cheap; Polyurethane binding, good springiness and soft and sticking, can be as acrylate adhesive dust in the energy absorbed air, dyefastness is better and be applicable to the stamp of knitted fabric again, but cost is higher, storage stability is relatively poor.Also have adhesive, vinegar third (vinylacetate and the acrylic ester copolymer) adhesive of elastomer silicone except above-mentioned three classes, but use seldom.
Development along with the COAT PRINTING technology, the polysiloxanes that it is found that excellent properties such as will having heat-resisting, weather-proof, hydrophobic, air-permeability, anti-oxidant, soft, smooth is introduced in the polyacrylic acid ester structure, can significantly improve flexibility, resistance to water, weatherability, anti-staining property and the elasticity etc. of polymer film.But, because the solubility parameter difference of polysiloxanes and polyacrylate is larger, cause its compatibility poor.Therefore, the exsertile Silicone acrylic emulsion not a duck soup of synthesizing stable and property.
The silicone-modified polyacrylate emulsion can realize by the method for conventional blend or copolymerization.The adhesive product that obtains of physical blending wherein, poor stability is used inconveniently, and it is lower that every application performance improves degree; And the organic-silicon-modified adhesive product that adopts copolymerization process to obtain, good stability, it is good with other component compatibilities of printing paste, and application performance improves obviously, particularly obviously improves the feel of PRINTED FABRIC, and every friction of while, brushing fastness are higher.Therefore, organosilicon modification by copolymerization macromolecular compound adhesive more and more is subject to people's attention.
Modification by copolymerization, different according to polymeric type, can be divided into again three kinds of bulk polymerization, polymerisation in solution and emulsion polymerisations.Wherein bulk polymerization is often used for preparing thick organosilicon inarch acrylate copolymer, and the condensation reaction by silicon hydroxyl and siloxy group or silicon acyloxy realizes crosslinked.Polymerisation in solution often utilizes polysiloxanes and polyacrylic acid to form block structure.Emulsion polymerization systems with water as continuous phase, avoided adopting solvent to make continuous phase to the pollution of environment, adopt the conventional emulsions copolymerization to prepare random, grafting, the block structure copolymer has been widely used in polysiloxane-modified polyacrylic acid technique, obtained the Silicone acrylic emulsion product of better performances, as CN1851112, prepared paint dyeing and printing adhesive agent by emulsion polymerization.
On the basis of conventional emulsion polymerization technology, coatings industry is in succession with core/shell emulsion technology, and the polymerization technique technology of latex interpenetrating polymerization innovation is applied to emulsion polymerisation, makes the performance of emulsion obtain improving largely.Wherein, the core-shell emulsion polymerization method receives people's concern always.At present at core-shell technique, emulsion particle somatometry of physique, emulsion particle particle shape, the research that affects the aspects such as mechanism of polymer performance has all been obtained remarkable progress, this has also further promoted the application of core-shell emulsion polymerization in the pigment printing binding agent field.70～eighties of last century, Sperling, the people such as L.H. adopt synthetic network-type (LIPN) the structure emulsion that passes mutually of emulsion polymerization first.The LIPN structure is different from simple blend, block or graft product, and it is being with rear three's notable difference on performance: (1) LIPN can swelling in solvent, but can not dissolve; (2) creep does not occur and flows in LIPN.Polysiloxanes and polyacrylic acid form the LIPN structure, realize polyacrylic modification, have obtained at present application achievements preferably.The Ziles of Dow corning company has synthesized the Polysiloxane/Polyacrylate functional latex with IPN structure with the seeded emulsion polymerization technology, this emulsion has good weather resisteant and hydrolytic resistance, has a extensive future in fields such as coating, adhesive, sealants.Nagarajan P, Mital CK, Trivedi M K.Latex interpenetrating polymer networks based on polyacrylates and polystyrene I.Synthetic variationd[J] .J ApplPolym Sci, 1996, (59): 191. adopt seeding polymerization method and swelling method to synthesize the PMMA/PSt emulsion of IPN structure, show that with DSC method measurement result compatibility both is very good.A lot of researchs about mutual biography network structure polymer have also been carried out over more domestic year, as standby in CN101245561 microemulsion legal system having obtained, interpenetrating network pigment resin printing adhesive agent.
Silicone modified polyacrylate is used by people as a kind of adhesive product of function admirable, but, organosilicon-modified acrylate class adhesive, the inherent shortcoming that also has itself result to determine on the problem that solves contradiction between adhesive feel and fastness.Silicone content is high, fabrics feel soft, but fastness reduction, and especially dry fastness is relatively poor; Silicone content is low, and feel is partially hard.Study new emulsion polymerization technique and complex process thereof, explore relevant theoretical question and will be from now on one period this field one of emphasis research topic.
Summary of the invention
The object of the invention is to provide a kind of research of silicone modified coating printing adhesive and preparation method thereof.
For achieving the above object, the present invention adopts technical scheme to be:
A kind of research of silicone modified coating printing adhesive, pigment printing binding agent are that low molecular weight organic silicon emulsion and unsaturated monomer carry out the organic-silicon-modified macromolecular compound of further copolyreaction gained as shown in general formula (I):
In formula:
M is selected from the integer of 1-10000;
N is selected from the integer of 1-500;
A, b are selected from respectively the integer of 0-500;
X is selected from one or more of group shown below:
R
1, R
2, R
3Can be identical or different, be selected from respectively hydrogen, C
1-C
10Alkyl, C
1-C
10Alkoxy or halogen;
R
4, R
5, R
6, R
7, R
8Can be identical or different, be selected from respectively C
1-C
10Alkyl, C
1-C
10Alkoxyl, C
2-C
10Alkylene, C
2-C
10Alkynes base, and R
4, R
5, R
6, R
7, R
8In have one at least for C
1-C
10Alkoxyl;
Be preferably compound shown in described general formula (I):
M is selected from the integer of 1-8000;
N is selected from the integer of 1-200;
A, b are selected from respectively the integer of 0-100;
X is selected from one or more of group shown below:
R
1, R
2, R
3Can be identical or different, be selected from respectively hydrogen, C
1-C
8Alkyl, C
1-C
8Alkoxy or halogen;
R
4, R
5, R
6, R
7, R
8Can be identical or different, be selected from respectively C
1-C
8Alkyl, C
1-C
8Alkoxyl, C
2-C
8Alkylene, C
2-C
8Alkynes base, and R
4, R
5, R
6, R
7, R
8In have one at least for C
1-C
8Alkoxyl;
Be preferably again compound shown in described general formula (I):
M is selected from the integer of 1-6000;
N is selected from the integer of 1-100;
A, b are selected from respectively the integer of 0-50;
X is selected from one or more of group shown below:
R
1, R
2, R
3Can be identical or different, be selected from respectively hydrogen, C
1-C
6Alkyl, C
1-C
6Alkoxy or halogen;
R
4, R
5, R
6, R
7, R
8Can be identical or different, be selected from respectively C
1-C
6Alkyl, C
1-C
6Alkoxyl, C
2-C
6Alkylene, C
2-C
6Alkynes base, and R
4, R
5, R
6, R
7, R
8In have one at least for C
1-C
6Alkoxyl;
Most preferably be compound shown in described general formula (I):
M is selected from the integer of 1-5000;
N is selected from the integer of 1-50;
A, b are selected from respectively the integer of 0-30;
X is selected from one or more of group shown below:
R
1, R
2, R
3Can be identical or different, be selected from respectively hydrogen, C
1-C
4Alkyl, C
1-C
4Alkoxy or halogen;
R
4, R
5, R
6, R
7, R
8Can be identical or different, be selected from respectively C
1-C
4Alkyl, C
1-C
4Alkoxyl, C
2-C
4Alkylene, C
2-C
4Alkynes base, and R
4, R
5, R
6, R
7, R
8In have one at least for C
1-C
4Alkoxyl;
The preparation method of research of silicone modified coating printing adhesive, at first with organosilicon ring body and silane end-cappers, then emulsification under Action of Surfactant add initator to carry out ring-opening polymerization, prepares the low molecular weight organic silicon emulsion;
With the low molecular weight organic silicon emulsion and the unsaturated monomer that prepare, carry out copolyreaction and obtain the research of silicone modified coating printing adhesive under surfactant, initator effect again.
In described low molecular weight organic silicon emulsion preparation method, described organosilicon ring body and silane end-cappers ring-opening polymerization, the mass ratio of organosilicon ring body and silane end-cappers is 1:0.001-0.5, and the reaction time is 0.5-8 hour, and reacts take water as reaction medium, under stirring; Reaction temperature 20-100 ℃.
Further, described organosilicon ring body and silane end-cappers ring-opening polymerization, the mass ratio of organosilicon ring body and silane end-cappers is 1:0.005-0.3; Reaction time is 2-5 hour; And react take water as reaction medium, under stirring; Reaction temperature 50-90 ℃.
In described research of silicone modified coating printing adhesive preparation method, described unsaturated monomer and the copolyreaction of low molecular weight organic silicon emulsion, the mass ratio 1:0.01-0.5 of unsaturated monomer and low molecular weight organic silicon emulsion, the time of reaction is 1-10 hour, and reacts take water as reaction medium, under stirring; Reaction temperature 20-100 ℃.
Further, described unsaturated monomer and the copolyreaction of low molecular weight organic silicon emulsion, the mass ratio of unsaturated monomer and low molecular weight organic silicon emulsion is 1:0.03-0.3; The time of reaction is 2-8 hour; And react take water as reaction medium, under stirring; Reaction temperature 40-90 ℃.
The application of research of silicone modified coating printing adhesive, organic-silicon-modified macromolecular compound shown in described general formula (I) can be used as the printing adhesive of pure cotton fabric or purifying fibre or BLENDED FABRIC.
The present invention has advantages of:
Pigment printing binding agent of the present invention is the research of silicone modified coating printing adhesive, organosilicon/acrylate complex emulsions by grafting modification, it shows splendid performance, can overcome that the palyacrylate binder fastness to wet rubbing is low, easy dust suction and sticking shortcoming of taking.Gained organosilicon modified acrylic ester binding agent of the present invention can obviously improve flexibility, ABRASION RESISTANCE and the corrosion resistance of COAT PRINTING fabric, and gives it and be difficult for the performances such as contamination.
The present invention is in the preparation process of low molecular weight organic silicon emulsion and research of silicone modified coating printing adhesive, to the improvement of emulsifying agent and polymerization technique aspect.Adopt reactive emulsifier, both improved the feel of fabric, improved again anti-dry-cleaning and water-wash resistance, especially application performance is outstanding on chemical ﹠ blended fabric, has solved the problem that general adhesive is not suitable for the chemical ﹠ blended fabric stamp; On synthesis technique, take soft monomer as core, hard monomer prepares printing adhesive as shell.Can be by changing the ratio of the inside and outside monomer of nucleocapsid, make that the inner layer glass transition temperature is high and the glass outer transition temperature is low, thereby obtain than the better film forming of common copolymer emulsion, stability and mechanical property.
The organic-silicon-modified polymer adhesive that the present invention prepares has extraordinary steady chemical structure, can form level and smooth, soft, have a flexible continuous film;
The organic-silicon-modified polymer adhesive that the present invention prepares both had been applicable to the stamp of pure cotton fabric, can be used for again the stamp of purifying fibre and BLENDED FABRIC;
The organic-silicon-modified polymer adhesive that the present invention prepares can be applicable to textile coating stamp, coating, and the outstanding caking property of condensate makes its printing area have outstanding feel and very high fastness (wetly rub, unlubricated friction fastness, washing fastness); Can also keep simultaneously soft feel, when especially being applied to deep printing, along with the increase of binder dosage, not produce stiffening feel.
Specific implementation method
Following examples are used for further illustrating the present invention, but the present invention only limits to absolutely not these embodiment.
Adhesive for COAT PRINTING of the present invention is organic-silicon-modified macromolecular compound adhesive, and concrete preparation method is as follows:
At first with organosilicon ring body and silane end-cappers, then emulsification under Action of Surfactant add initator to carry out ring-opening polymerization, prepares the low molecular weight organic silicon emulsion.
With the low molecular weight organic silicon emulsion and the unsaturated monomer that prepare, carry out copolyreaction and obtain research of silicone modified coating printing adhesive (research of silicone modified coating printing adhesive) under surfactant, initator effect again.
Described organosilicon ring body is selected from but is not limited to one or more of octamethylcy-clotetrasiloxane (D4), hexamethyl cyclotrisiloxane (D3), decamethylcyclopentaandoxane (D5), tetramethyl tetrem thiazolinyl cyclotetrasiloxane (V4), trimethyl trivinyl cyclotrisiloxane (V3), pentamethyl five vinyl D5s (V5); Described silane end-cappers is selected from but is not limited to HMDO, tetramethoxy-silicane, tetraethoxysilane, tetramethyl divinyl disiloxane, vinyltrimethoxy silane, vinyltriethoxysilane, 3-(methacryloxypropyl) one or more of propyl trimethoxy silicane (A-174) or vinyl three (2-methoxy ethoxy) silane (A-172).
Described unsaturated monomer is selected from but is not limited to one or more in the unsaturated monomers such as methyl methacrylate, styrene, vinyl acetate, vinyl chloride, acrylonitrile, methyl vinyl ketone, vinyl pyrrolidone, acrylic acid, methyl butene base ketone, acrylamide, n-methylolacrylamide, ethoxy acrylamide, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethyl hexyl acrylate.
The conditions such as the kind by controlling initator and surfactant in course of reaction and consumption, reaction temperature, reaction time, each raw material rate of charge, obtain having the polymerizate of the suitable degree of polymerization, mean molecule quantity and solid content, thereby obtain the pigment printing binding agent of every application performance excellences such as super soft, dried, wet friction and brushing fastness.
Described initiator amount accounts for reaction system mass percent 0.005-10%, preferred 0.1-5%; Initator can be selected from ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, hydrogen peroxide, benzoyl peroxide, cyclohexanone peroxide, tert-butyl hydroperoxide, N, N, N ', one or more any combination in N '-tetramethylethylenediamine, azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile).
Described dosage of surfactant accounts for reaction system mass percent 0.05-15%, preferred 0.1-5%.surfactant is selected from odium stearate, enuatrol, sodium laurate, lauryl sodium sulfate, sldium lauryl sulfate, neopelex, the dioctyl sodium succinate (A Luosuo-OT), sodium glycocholate, monoethanolamine, diethanol amine, triethanolamine, quaternary ammonium salt, imidazoline, moroxydine, triazine derivative, amino acid, betaine, tristerin, sucrose ester, this class class, Tweens, OPEO, the alkylphenol polyoxyethylene such as polyoxyethylene nonylphenol ether, high-carbon fatty alcohol polyoxyethylene ether (AEO), polyoxyethylene carboxylate (AE), polyoxyethylene amine, polyoxyethylate amide, the anion such as sorbitan ester, CATION, one or more any combination in both sexes and non-ionic surface active agent.
If no special instructions, percentage composition and umber unit in embodiment are quality.The raw materials used natrium carbonicum calcinatum of following examples, DBSA, acrylamide, Methacrylamide, methyl methacrylate, glycidyl methacrylate, acrylic acid, acrylonitrile, butyl acrylate, ethyl acrylate, ammonium persulfate are AR, purchase in traditional Chinese medicines group's chemical reagent Shenyang Co., Ltd; Octamethylcy-clotetrasiloxane, tetramethyl tetrem thiazolinyl cyclotetrasiloxane, Dow corning; Vinyltriethoxysilane, A-172, A-174, Kaihua County brothers' silicone material factory; The ethoxy acrylamide, Shanghai abundant chemical industry Co., Ltd; Crosslinking agent NF, Yizhong, Zibo City chemical industry Co., Ltd; OS-15, Liaoning chemical industry joint-stock company of group of Huaxing; DP-20s, the great chemical industry of upper starfish Co., Ltd; AEO-7, Shenzhen Haichuan Chemical Technology Co., Ltd.Each embodiment performance detects instrument: Ubbelohde viscometer, PHSJ-4A type pH meter (Shanghai Precision Scientific Apparatus Co., Ltd), Y571B colorfastness to rubbing instrument (Nantong grand laboratory apparatus Co., Ltd).Normative reference: GB/T10664-2003, GB/T3920-2008, GB/T420-2009, GB/T1725-2007, GB/T14518-1993.
Embodiment first: the organosilyl preparation of low molecular weight
Embodiment 1
in with the four-hole bottle that stirs, 2.06 parts of DBSAs are joined in 250 parts of water, heating is dissolved it fully, then be cooled to room temperature, passed into nitrogen 15 minutes, add 122.06 parts of octamethylcy-clotetrasiloxanes under rapid stirring, 3.9 parts of vinyltriethoxysilane, after adding, rapid stirring emulsification 1h, emulsification is complete, mixing speed slows down, begin heating, be heated to 85 ℃, insulation reaction 3 hours, then be cooled to room temperature, be neutralized to the pH=7 left and right with 10% sodium carbonate liquor, with 100 order nylon net filter dischargings, obtain low molecular weight organic silicon emulsion IA, pH value 7.12, gel fraction 2.07%, conversion ratio 96.42%, structural formula is:
It is 0 that a is about 10, b; R, R
8Be vinyl, R
4, R
5, R
6, R
7Be ethyoxyl;
Embodiment 2
in with the four-hole bottle that stirs, with 2.06 parts of DBSAs, 0.5 a part AEO-7 joins in 250 parts of water, heating is dissolved it fully, then be cooled to room temperature, passed into nitrogen 15 minutes, add 102.06 parts of octamethylcy-clotetrasiloxanes under rapid stirring, 20 parts of tetramethyl tetrem thiazolinyl cyclotetrasiloxanes, 3.9 parts of vinyltriethoxysilane, after adding, rapid stirring emulsification 1h, emulsification is complete, mixing speed slows down, begin heating, be heated to 85 ℃, insulation reaction 3 hours, then be cooled to room temperature, be neutralized to the pH=7 left and right with 10% sodium carbonate liquor, with 100 order nylon net filter dischargings, obtain low molecular weight organic silicon emulsion IIA, , pH value 7.08, gel fraction 2.13%, conversion ratio 96.47%.
Structural formula is:
A is about 8, b and is about 1;
R, R
8Be vinyl, R
4, R
5, R
6, R
7Be ethyoxyl;
Embodiment 3
in with the four-hole bottle that stirs, 2.06 parts of DBSAs are joined in 250 parts of water, heating is dissolved it fully, then be cooled to room temperature, passed into nitrogen 15 minutes, add 122.06 parts of octamethylcy-clotetrasiloxanes under rapid stirring, A-1723.9 part, after adding, rapid stirring emulsification 1h, emulsification is complete, mixing speed slows down, begin heating, be heated to 85 ℃, insulation reaction 3 hours, then be cooled to room temperature, be neutralized to the pH=7 left and right with 10% sodium carbonate liquor, with 100 order nylon net filter dischargings, obtain low molecular weight organic silicon emulsion IIIA, pH value 7.10, gel fraction 1.94%, conversion ratio 96.72%.
Structural formula is:
It is 0 that a is about 13, b; R, R
8Be vinyl, R
4, R
5, R
6, R
7Be the 'beta '-methoxy ethyoxyl;
Embodiment 4
in with the four-hole bottle that stirs, 2.06 parts of DBSAs are joined in 250 parts of water, heating is dissolved it fully, then be cooled to room temperature, passed into nitrogen 15 minutes, add 122.06 parts of octamethylcy-clotetrasiloxanes under rapid stirring, A-1722.9 part, A-1741 part, after adding, rapid stirring emulsification 1h, emulsification is complete, mixing speed slows down, begin heating, be heated to 85 ℃, insulation reaction 3 hours, then be cooled to room temperature, be neutralized to the pH=7 left and right with 10% sodium carbonate liquor, with 100 order nylon net filter dischargings, obtain low molecular weight organic silicon emulsion IVA, pH value 7.12, gel fraction 2.05%, conversion ratio 96.77%.
Structural formula is:
It is 0 that a is about 13, b;
R, R
8Be selected from vinyl and/or γ-(Methacrylamide oxygen base)-propyl group, R
4Be selected from 'beta '-methoxy ethyoxyl and/or methoxyl group, R
5Be selected from 'beta '-methoxy ethyoxyl and/or methoxyl group, R
6Be selected from 'beta '-methoxy ethyoxyl and/or methoxyl group, R
7Be selected from 'beta '-methoxy ethyoxyl and/or methoxyl group;
Embodiment second portion: the preparation of research of silicone modified coating printing adhesive
Embodiment 5
2.5g OS-15,2.5g DP-20S heating for dissolving in 30g water, are joined it with in the 500ml there-necked flask that stirs after cooling; Add material butyl acrylate 62g, acrylic acid 5g, methyl methacrylate 2g, acrylonitrile 10g and low molecular weight organic silicon emulsion IA18g again in there-necked flask;
1.5g glycidyl methacrylate and 0.2g ammonium persulfate are dissolved in respectively in 15g water, after dissolve complete, it are added in above-mentioned there-necked flask, and add 50g water in there-necked flask, rapid stirring emulsification 30 minutes, stand-by;
Get the white emulsion 15g that above-mentioned emulsification obtains, join in the 500ml there-necked flask of another with heating and stirring, start stirring, begin heating, be heated to 85 ℃, insulation reaction 10min;
1.5g glycidyl methacrylate and 0.3g ammonium persulfate are dissolved in respectively in 20g water, after dissolve complete, it is joined in remaining emulsion and mix, be added drop-wise to after mixing in the there-necked flask of above-mentioned white emulsion, keep temperature and 85 ℃, control rate of addition, 2.5h dropwises; After dropwising, then insulation reaction 3h, is cooled to room temperature, then to add 25% ammonia neutralization be 7 left and right to reactant liquor pH, 100 order nylon net filters, and discharging obtains white research of silicone modified coating printing adhesive IBa, and molecular weight is about 3.0*10
5, solid content 43.14%, pH value 7.54, gel fraction 3.17%, conversion ratio 95.38%.
Structural formula is:
M is about 2300, n and is about 20, a to be about 10, b be 0;
R
1, R
2, R
3Be hydrogen, R
4, R
5, R
6, R
7Be ethyoxyl, R
8Be vinyl;
X is group shown below:
Embodiment 6
2.5g OS-15,2.5g DP-20S heating for dissolving in 30g water, are joined it with in the 500ml there-necked flask that stirs after cooling; Add material butyl acrylate 62g, acrylic acid 5g, methyl methacrylate 2g, acrylonitrile 10g, low molecular weight organic silicon emulsion IIA18g again in there-necked flask;
1.5g glycidyl methacrylate and 0.2g ammonium persulfate are dissolved in respectively in 15g water, after dissolve complete, it are added in there-necked flask, and add 50g water in there-necked flask, rapid stirring emulsification 30 minutes, stand-by;
Get the white emulsion 15g that above-mentioned emulsification obtains, join in the 500ml there-necked flask of another with heating and stirring, start stirring, begin heating, be heated to 85 ℃, insulation reaction 10min;
1.5g glycidyl methacrylate and 0.3g ammonium persulfate are dissolved in respectively in 20g water, after dissolve complete, it is joined in remaining emulsion and mix, be added drop-wise to after mixing in the there-necked flask of above-mentioned white emulsion, keep temperature and 85 ℃, control rate of addition, 2.5h dropwises; After dropwising, then insulation reaction 3h, is cooled to room temperature, then to add 25% ammonia neutralization be 7 left and right to reactant liquor pH, 100 order nylon net filters, and discharging obtains white research of silicone modified coating printing adhesive IIB, and structural formula is:
M is about 2650, n and is about 23, a to be about 8, b be 1;
R
1, R
2, R
3Be hydrogen, R
4, R
5, R
6, R
7Be ethyoxyl, R
8Be vinyl;
X is group shown below:
Molecular weight is about 3.5*10
5, solid content 43.17%, pH value 7.62, gel fraction 3.02%, conversion ratio 95.41%.
Embodiment 7
2.5g OS-15,2.5g DP-20S heating for dissolving in 30g water, are joined it with in the 500ml there-necked flask that stirs after cooling; Add material butyl acrylate 62g, acrylic acid 5g, methyl methacrylate 2g, acrylonitrile 10g, low molecular weight organic silicon emulsion IIIA18g again in there-necked flask;
1.5g glycidyl methacrylate and 0.2g ammonium persulfate are dissolved in respectively in 15g water, after dissolve complete, it are added in above-mentioned there-necked flask, and add 50g water in there-necked flask, rapid stirring emulsification 30 minutes, stand-by;
Get the white emulsion 15g that above-mentioned emulsification obtains, join in the 500ml there-necked flask of another with heating and stirring, start stirring, begin heating, be heated to 85 ℃, insulation reaction 10min;
1.5g glycidyl methacrylate and 0.3g ammonium persulfate are dissolved in respectively in 20g water, after dissolve complete, it is joined in remaining emulsion and mix, be added drop-wise to after mixing in the there-necked flask of above-mentioned white emulsion, keep temperature and 85 ℃, control rate of addition, 2.5h dropwises; After dropwising, then insulation reaction 3h, is cooled to room temperature, then to add 25% ammonia neutralization be 7 left and right to reactant liquor pH, 100 order nylon net filters, and discharging obtains white research of silicone modified coating printing adhesive IIIB, and structural formula is:
M is about 1800, n and is about 16, a to be about 13, b be 0;
R
1, R
2, R
3Be hydrogen, R
4, R
5, R
6, R
7Be 'beta '-methoxy ethyoxyl, R
8Be vinyl;
X is group shown below:
Molecular weight is about 2.4*10
5, solid content 43.08%, pH value 7.61, gel fraction 3.05%, conversion ratio 95.41%.
Embodiment 8
2.5g OS-15,2.5g DP-20S heating for dissolving in 30g water, are joined it with in the 500ml there-necked flask that stirs after cooling; Add material butyl acrylate 62g, acrylic acid 5g, methyl methacrylate 2g, acrylonitrile 10g, low molecular weight organic silicon emulsion IVA18g again in there-necked flask;
1.5g glycidyl methacrylate and 0.2g ammonium persulfate are dissolved in respectively in 15g water, after dissolve complete, it are added in there-necked flask, and add 50g water in there-necked flask, rapid stirring emulsification 30 minutes, stand-by;
Get the white emulsion 15g that above-mentioned emulsification obtains, join in the 500ml there-necked flask of another with heating and stirring, start stirring, begin heating, be heated to 85 ℃, insulation reaction 10min;
1.5g glycidyl methacrylate and 0.3g ammonium persulfate are dissolved in respectively in 20g water, after dissolve complete, it is joined in remaining emulsion and mix, be added drop-wise to after mixing in the there-necked flask of above-mentioned white emulsion, keep temperature and 85 ℃, control rate of addition, 2.5h dropwises; After dropwising, then insulation reaction 3h, is cooled to room temperature, then to add 25% ammonia neutralization be 7 left and right to reactant liquor pH, 100 order nylon net filters, and discharging obtains white research of silicone modified coating printing adhesive IVB, and molecular weight is about 3.2*10
5, solid content 43.05%, pH value 7.57, gel fraction 3.02%, conversion ratio 95.37%.
Structural formula is:
M is about 2150, n and is about 19, a to be about 13, b be 0;
R
1, R
2, R
3Be hydrogen, R
4, R
5Be 'beta '-methoxy ethyoxyl, R
6, R
7Be methoxyl group, R
8Be γ-(Methacrylamide oxygen base)-propyl group;
X is group shown below:
Embodiment 9
2.5g OS-15,2.5g DP-20S heating for dissolving in 30g water, are joined it with in the 500ml there-necked flask that stirs after cooling; Add material ethyl acrylate 62g, methacrylic acid 5g, methyl methacrylate 2g, acrylonitrile 10g, low molecular weight organosilicon IA18g again in there-necked flask;
1.5g acrylamide and 0.2g ammonium persulfate are dissolved in respectively in 15g water, after dissolve complete, it are added in there-necked flask, and add water 50g in there-necked flask, rapid stirring emulsification 30 minutes, stand-by;
Get the white emulsion 15g that above-mentioned emulsification obtains, join in the 500ml there-necked flask of another with heating and stirring, start stirring, begin heating, be heated to 85 ℃, insulation reaction 10min;
1.5g acrylamide and 0.3g ammonium persulfate are dissolved in respectively in 20g water, after dissolve complete, it is joined in remaining emulsion and mix, be added drop-wise to after mixing in the there-necked flask of above-mentioned white emulsion, keep temperature and 85 ℃, control rate of addition, 2.5h dropwises; After dropwising, then insulation reaction 3h, is cooled to room temperature, then to add 25% ammonia neutralization be 7 left and right to reactant liquor pH, 100 order nylon net filters, and discharging obtains white research of silicone modified coating printing adhesive IBb, and molecular weight is about 3.2*10
5, solid content 43.11%, pH value 7.58, gel fraction 3.10%, conversion ratio 95.35%.
Structural formula is:
M is about 3100, n and is about 23, a to be about 10, b be 0;
R
1, R
2, R
3Be hydrogen, R
4, R
5, R
6, R
7Be ethyoxyl, R
8Be vinyl;
X is group shown below:
Embodiment 10
2.5g OS-15,2.5g DP-20S heating for dissolving in 30g water, are joined it with in the 500ml there-necked flask that stirs after cooling; Add material butyl acrylate 62g, acrylic acid 5g, styrene 2g, acrylonitrile 10g, low molecular weight organosilicon IA18g again in there-necked flask;
1.5g Methacrylamide and 0.2g ammonium persulfate are dissolved in respectively in 15g water, after dissolve complete, it are added in there-necked flask, and add 50g water in there-necked flask, rapid stirring emulsification 30 minutes, stand-by;
Get the white emulsion 15g that above-mentioned emulsification obtains, join in the 500ml there-necked flask of another with heating and stirring, start stirring, begin heating, be heated to 85 ℃, insulation reaction 10min;
1.5g Methacrylamide and 0.3g ammonium persulfate are dissolved in respectively in 20g water, after dissolve complete, it is joined in remaining emulsion and mix, be added drop-wise to after mixing in the there-necked flask of above-mentioned white emulsion, keep temperature and 85 ℃, control rate of addition, 2.5h dropwises; After dropwising, then insulation reaction 3h, is cooled to room temperature, then to add 25% ammonia neutralization be 7 left and right to reactant liquor pH, 100 order nylon net filters, and discharging obtains white research of silicone modified coating printing adhesive IBc, and molecular weight is about 4.6*10
5, solid content 43.17%, pH value 7.62, gel fraction 3.13%, conversion ratio 95.37%.
Structural formula is:
M is about 3500, n and is about 30, a to be about 10, b be 0;
R
1, R
2, R
3Be hydrogen, R
4, R
5, R
6, R
7Be ethyoxyl, R
8Be vinyl;
X is group shown below:
Embodiment 11
2.5g OS-15,2.5g DP-20S heating for dissolving in 30g water, are joined it with in the 500ml there-necked flask that stirs after cooling; Add material butyl acrylate 40g, ethyl acrylate 22g, acrylic acid 5g, styrene 2g, acrylonitrile 10g, low molecular weight organosilicon IA18g again in there-necked flask;
Respectively with the 1.5gN-(2-ethoxy) acrylamide and 0.2g ammonium persulfate be dissolved in respectively in 15g water, and after dissolve complete, it is added in there-necked flask, and add 50g water in there-necked flask, rapid stirring emulsification 30 minutes, stand-by;
Get the white emulsion 15g that above-mentioned emulsification obtains, join in the 500ml there-necked flask of another with heating and stirring, start stirring, begin heating, be heated to 85 ℃, insulation reaction 10min;
With the 1.5gN-(2-ethoxy) acrylamide and 0.3g ammonium persulfate be dissolved in respectively in 20g water, after dissolve complete, it is joined in remaining emulsion and mix, be added drop-wise to after mixing in the there-necked flask of above-mentioned white emulsion, keep temperature and 85 ℃, control rate of addition, 2.5h dropwises; After dropwising, then insulation reaction 3h, is cooled to room temperature, then to add 25% ammonia neutralization be 7 left and right to reactant liquor pH, 100 order nylon net filters, and discharging obtains white research of silicone modified coating printing adhesive IBd, and molecular weight is about 4.8*10
5, solid content 43.08%, pH value 7.61, gel fraction 3.07%, conversion ratio 95.42%.
Structural formula is:
M is about 3650, n and is about 31, a to be about 10, b be 0;
R
1, R
2, R
3Be hydrogen, R
4, R
5, R
6, R
7Be ethyoxyl, R
8Be vinyl;
X is group shown below:
Embodiment third part: organic-silicon-modified macromolecular compound adhesive application performance test
A. application performance test formulations:
B. printing technology condition:
Stamp → 100 ℃ of oven dry (3min) → bake (160 ℃ of temperature, 3min)
Applied performance analysis is analyzed according to GB/T250-2008, GB/T420-2009, GB/T3921-2008.Wherein, pliability: by from firmly being divided into 1,2,3,4,5 grade to soft order; Do, wet-milling rubbing fastness and brushing fastness also be divided into 1,2,3,4,5 grade according to GB.
Claims (10)
1. research of silicone modified coating printing adhesive, it is characterized in that: pigment printing binding agent is that low molecular weight organic silicon emulsion and unsaturated monomer carry out the organic-silicon-modified macromolecular compound of further copolyreaction gained, as shown in general formula (I):
In formula:
M is selected from the integer of 1-10000;
N is selected from the integer of 1-500;
A, b are selected from respectively the integer of 0-500;
X is selected from one or more of group shown below:
R
1, R
2, R
3Can be identical or different, be selected from respectively hydrogen, C
1-C
10Alkyl, C
1-C
10Alkoxy or halogen;
R
4, R
5, R
6, R
7, R
8Can be identical or different, be selected from respectively C
1C
10Alkyl, C
1-C
10Alkoxyl, C
2-C
10Alkylene, C
2-C
10Alkynes base, and R
4, R
5, R
6, R
7, R
8In have one at least for C
1-C
10Alkoxyl.
2. by research of silicone modified coating printing adhesive claimed in claim 1, it is characterized in that: compound shown in described general formula (I):
M is selected from the integer of 1-8000;
N is selected from 1200 integer;
A, b are selected from respectively the integer of 0-100;
X is selected from one or more of group shown below:
R
1, R
2, R
3Can be identical or different, be selected from respectively hydrogen, C
1-C
8Alkyl, C
1-C
8Alkoxy or halogen;
R
4, R
5, R
6, R
7, R
8Can be identical or different, be selected from respectively C
1-C
8Alkyl, C
1-C
8Alkoxyl, C
2-C
8Alkylene, C
2-C
8Alkynes base, and R
4, R
5, R
6, R
7, R
8In have one at least for C
1-C
8Alkoxyl.
3. by research of silicone modified coating printing adhesive claimed in claim 2, it is characterized in that: compound shown in described general formula (I):
M is selected from the integer of 1-6000;
N is selected from the integer of 1-100;
A, b are selected from respectively the integer of 0-50;
X is selected from one or more of group shown below:
R
1, R
2, R
3Can be identical or different, be selected from respectively hydrogen, C
1-C
6Alkyl, C
1-C
6Alkoxy or halogen;
R
4, R
5, R
6, R
7, R
8Can be identical or different, be selected from respectively C
1-C
6Alkyl, C
1-C
6Alkoxyl, C
2-C
6Alkylene, C
2-C
6Alkynes base, and R
4, R
5, R
6, R
7, R
8In have one at least for C
1-C
6Alkoxyl.
4. by research of silicone modified coating printing adhesive claimed in claim 3, it is characterized in that: compound shown in described general formula (I):
M is selected from the integer of 1-5000;
N is selected from the integer of 1-50;
A, b are selected from respectively the integer of 0-30;
X is selected from one or more of group shown below:
R
1, R
2, R
3Can be identical or different, be selected from respectively hydrogen, C
1-C
4Alkyl, C
1-C
4Alkoxy or halogen;
R
4, R
5, R
6, R
7, R
8Can be identical or different, be selected from respectively C
1-C
4Alkyl, C
1-C
4Alkoxyl, C
2-C
4Alkylene, C
2-C
4Alkynes base, and R
4, R
5, R
6, R
7, R
8In have one at least for C
1-C
4Alkoxyl.
5. the preparation method of a research of silicone modified coating printing adhesive claimed in claim 1, it is characterized in that: at first with organosilicon ring body and silane end-cappers, then emulsification under Action of Surfactant add initator to carry out ring-opening polymerization, prepares the low molecular weight organic silicon emulsion;
With the low molecular weight organic silicon emulsion and the unsaturated monomer that prepare, carry out copolyreaction and obtain the research of silicone modified coating printing adhesive under surfactant, initator effect again.
6. press the preparation method of research of silicone modified coating printing adhesive claimed in claim 5, it is characterized in that: in described low molecular weight organic silicon emulsion preparation method, described organosilicon ring body and silane end-cappers ring-opening polymerization, the mass ratio of organosilicon ring body and silane end-cappers is 1:0.001-0.5, reaction time is 0.5-8 hour, and reacts take water as reaction medium, under stirring; Reaction temperature 20-100 ℃.
7. by the preparation method of research of silicone modified coating printing adhesive claimed in claim 6, it is characterized in that:
In described low molecular weight organic silicon emulsion preparation method, described organosilicon ring body and silane end-cappers ring-opening polymerization, the mass ratio of organosilicon ring body and silane end-cappers is 1:0.005-0.3; Reaction time is 2-5 hour; And react take water as reaction medium, under stirring; Reaction temperature 50-90 ℃.
8. by the preparation method of research of silicone modified coating printing adhesive claimed in claim 5, it is characterized in that:
In described research of silicone modified coating printing adhesive preparation method, described unsaturated monomer and the copolyreaction of low molecular weight organic silicon emulsion, the mass ratio 1:0.01-0.5 of unsaturated monomer and low molecular weight organic silicon emulsion, the time of reaction is 1-10 hour, and reacts take water as reaction medium, under stirring; Reaction temperature 20-100 ℃.
9. press the preparation method of research of silicone modified coating printing adhesive claimed in claim 8, it is characterized in that: in described research of silicone modified coating printing adhesive preparation method, described unsaturated monomer and the copolyreaction of low molecular weight organic silicon emulsion, the mass ratio of unsaturated monomer and low molecular weight organic silicon emulsion is 1:0.03-0.3; The time of reaction is 2-8 hour; And react take water as reaction medium, under stirring; Reaction temperature 40-90 ℃.
10. the application of a research of silicone modified coating printing adhesive claimed in claim 1 is characterized in that: organic-silicon-modified macromolecular compound shown in described general formula (I) can be used as the printing adhesive of pure cotton fabric or purifying fibre or BLENDED FABRIC.
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| CN105017493A (en) * | 2014-04-15 | 2015-11-04 | 辽宁天麒科技有限公司 | Organosilicon-modified poor solvent ink-absorption coating resin, preparation method and applications thereof |
| CN105324687A (en) * | 2013-06-28 | 2016-02-10 | 横滨橡胶株式会社 | Resin compositions for forming hard coating layer |
| CN105755864A (en) * | 2016-02-29 | 2016-07-13 | 广西大学 | Method for preparing printing coating adhesive |
| CN112661895A (en) * | 2020-12-23 | 2021-04-16 | 江南大学 | Preparation method of chemical crosslinking type monodisperse colored latex particles |
| CN114805426A (en) * | 2022-01-07 | 2022-07-29 | 山东硅科新材料有限公司 | Modified vinyl silane and preparation method and application thereof |
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| CN102796230A (en) * | 2011-05-24 | 2012-11-28 | 武汉强力荷新材料有限公司 | Method for preparing silicone acrylic emulsion with high solid content and high silicon content |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105324687A (en) * | 2013-06-28 | 2016-02-10 | 横滨橡胶株式会社 | Resin compositions for forming hard coating layer |
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| CN105755864A (en) * | 2016-02-29 | 2016-07-13 | 广西大学 | Method for preparing printing coating adhesive |
| CN112661895A (en) * | 2020-12-23 | 2021-04-16 | 江南大学 | Preparation method of chemical crosslinking type monodisperse colored latex particles |
| CN112661895B (en) * | 2020-12-23 | 2023-03-24 | 江南大学 | Preparation method of chemical crosslinking type monodisperse colored latex particles |
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