CN105924597A - Amphiphilic polymer with T-shaped or pi-shaped structure and synthesizing method of amphiphilic polymer - Google Patents
Amphiphilic polymer with T-shaped or pi-shaped structure and synthesizing method of amphiphilic polymer Download PDFInfo
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- CN105924597A CN105924597A CN201610317856.0A CN201610317856A CN105924597A CN 105924597 A CN105924597 A CN 105924597A CN 201610317856 A CN201610317856 A CN 201610317856A CN 105924597 A CN105924597 A CN 105924597A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/04—Polymers provided for in subclasses C08C or C08F
- C08F290/046—Polymers of unsaturated carboxylic acids or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/061—Polyesters; Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
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Abstract
The invention discloses an amphiphilic polymer with the T-shaped or pi-shaped structure and a synthesizing method of the amphiphilic polymer. A molecular main chain of the amphiphilic polymer is a vinyl polymer with one or more than one polar group, and a side chain of the amphiphilic polymer is a graft polymer which is composed of one or two oleophilic polymers and has the T-shaped or pi-shaped structure. The amphiphilic polymer which is invented according to the free radical copolymerization principle and has the T-shaped or pi-shaped structure is simple in synthesizing process, wide in raw material source and low in cost. By synthesizing the polymer through the method, the number-average molecular weight can be freely controlled to be within the range from 3,000 to 10,000, and the amphiphilic polymer has the wide application prospect in the field of coating and ink.
Description
Technical field
The present invention relates to coating and resin for printing ink field, more specifically to solvent based coating auxiliary agent and preparation method thereof.
Background technology
Pigment mainly exists with forms such as aggregation, agglomerate or floccule bodys, and granule is thick and skewness, causes the colour brightness of pigment and vividness poor.Pigment, as coloring agent, the most uniformly, is dispersed stably in medium, could well play its pigmentation.For solving the problems referred to above, current commonly used nonionic, anion, cationic surfactant and some low molecule or polymer confrontation surface of pigments are modified.AB block type pigment dispersing agent is exactly the macromolecule hyper-dispersant of a kind of excellent performance.The highest attention of coating and ink industry it has been constantly subjected to since this kind of dispersant occurs in the eighties in last century.
The present invention is attempted with molecule chain end to be had the polymer of single-ended vinyl and carries out radical solution copolymerization containing the vinyl monomer of polar group, forms the macromolecule hyper-dispersant being similar to AB block type macromole.When utilizing the dispersion of this hyper-dispersant organic with inorganic pigment, solid content height, good fluidity, dispersion that stability is high can be obtained.
Summary of the invention
It is an object of the invention to provide a kind of synthesis technique simple, raw material sources have the T-shaped or amphiphilic polymers of π type structure and synthetic method thereof widely.
The technical solution of the present invention is:
A kind of have the T-shaped or amphiphilic polymers of π type structure, it is characterized in that: the molecular backbone of described amphiphilic polymers is the polyvinyl of the polar group with one or more, side chain is had the T-shaped or graft polymers of π type structure by what one or two oil loving polymer formed.
The synthetic method of a kind of amphiphilic polymers with T-shaped or π type structure, is characterized in that:
1) in the presence of an organic by a kind of or two kinds carry out radical solution copolymerization reaction together containing the vinyl monomer of polar group, single-ended polyvinyl polymeric monomer, chain-transferring agent, polymeric reaction temperature is 80 ~ 170 DEG C, response time controls at 3 ~ 15 hours, to ensure that the conversion ratio of polyreaction reaches 100%；Course of reaction is gradually added radical polymerization initiator, the consumption of radical polymerization initiator is the 0.1% ~ 10% of vinyl monomer gross mass, the consumption of chain-transferring agent is the 0.1% ~ 10% of vinyl monomer gross mass, obtains described having the T-shaped or amphiphilic polymers solution of π type structure；
2) during the organic solvent used in polyreaction is benzene,toluene,xylene, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butyl glycol ether, N-Methyl pyrrolidone any one or several, consumption of organic solvent is the 30% ~ 200% of vinyl monomer gross mass.
Vinyl monomer containing polar group is acrylic acid, methacrylic acid, acrylamide, Methacrylamide, hydroethyl acrylate, β-hydroxy propyl acrylate, methacrylic acid β hydroxyl ethyl ester, methacrylic acid β hydroxypropyl acrylate, acrylic acid (N, N-dimethyl amido) ethyl ester, methacrylic acid (N, N-dimethyl amido) ethyl ester, more than one or more than one monomer in maleic anhydride, the number-average molecular weight of main chain controls within 500 to 2000.
Described single-ended polyvinyl is one-ended hydroxy polymer, single-ended carboxyl polymer, single-ended epoxy-based polymerization thing or single-ended amine based polymer (number-average molecular weight of polymer all controls in the range of 500 to 3000) and glycidyl acrylate, glycidyl methacrylate, hydroethyl acrylate, β-hydroxy propyl acrylate, methacrylic acid β hydroxyl ethyl ester, methacrylic acid β hydroxypropyl acrylate, 1-chloro-4-methyl-benzene, acrylic acid, a kind of monomer in methacrylic acid is formed by high molecular weight reactive, in order to prevent vinyl monomer auto polymerization in organic reaction, reaction is added total monomer weight 100,000/to the polymerization inhibitor of one thousandth amount.
Described chain-transferring agent is lauryl mercaptan, n-butyl mercaptan, 3-isooctyl mercaptopropionate or TPMS.
Described radical polymerization initiator is initiator or the per-compound type initiator of azo-type.
Described azo-type initiator is azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile) or 4,4'-azo (4-cyanopentanoic acid).
Described per-compound type initiator is dibenzoyl peroxide, dilauroyl peroxide, cyclohexanone peroxide, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, the benzoyl peroxide tert-butyl ester, the peroxidating trimethylacetic acid tert-butyl ester, t-amyl peroxy hydrogen, two tertiary amyl peroxide, 1.1-(di-tert-butyl peroxide) thiacyclohexane or the peroxidating pivalic acid tert-butyl ester.
The present invention is T-shaped according to having of inventing of the principle of radical copolymerization or the synthesis technique of the amphiphilic polymers of π type structure is simple, and raw material sources are extensive, with low cost.Utilizing the method synthetic polymer, its number-average molecular weight can freely control the scope 2000 to 10000, is with a wide range of applications with ink area at coating.
Below in conjunction with embodiment, the invention will be further described.
Detailed description of the invention
Embodiment 1
In there is reflux condenser, agitator, the temperature display controller reactor with charging Dropping funnel, add 20 grams of the single-ended carboxy acrylic ester type polymer that number-average molecular weight is 2000, and add the glycidyl fat of equimolar amounts, catalyst 4 bromide, hydroquinone of polymerization retarder and solvent butyl acetate according to the acid number of resin, continue after being warming up to 130 DEG C to react 5 hours at such a temperature.After reaction terminates, add 5 grams of hydroethyl acrylates, 3 lauryl mercaptans, under agitation it is warming up to reflux temperature and continues backflow 1 hour at such a temperature, after backflow terminates, continue under stirring condition with reflux temperature, add, through Dropping funnel, the solution that a certain amount of azodiisobutyronitrile, butyl acetate and monomeric acrylic β hydroxyl ethyl ester are formed in 3 hours, back flow reaction is continued 1 hour after being added dropwise to complete, add the propylene glycol monomethyl ether solution of azodiisobutyronitrile the most in three times, every minor tick 1 hour, continues reaction 1 hour after initiator solution adds for the third time.At this moment define main chain be with hydroxyl polar group side chain be acrylate based polymer there is the T-shaped or amphiphilic polymers of π type structure.This polymer has good dispersibility and dispersion stabilization to flatting silica.
Embodiment 2
In there is reflux condenser, agitator, the temperature display controller reactor with charging Dropping funnel, add 20 grams of the single-ended carboxy acrylic ester type polymer that number-average molecular weight is 2000, and add the methyl propenoic acid glycidyl fat of equimolar amounts, catalyst 4 bromide, hydroquinone of polymerization retarder and solvent butyl acetate according to the acid number of resin, continue after being warming up to 130 DEG C to react 5 hours at such a temperature.After reaction terminates, add 5 grams of acrylic acid (N, N-dimethyl amido) ethyl ester, 3 lauryl mercaptans, under agitation it is warming up to reflux temperature and continues to reflux 1 hour under counterflow condition at such a temperature, after backflow terminates, continue under stirring condition with reflux temperature, a certain amount of benzoyl peroxide is added through Dropping funnel in 3 hours, butyl acetate and acrylic acid (N, N dimethyl amido) solution that formed of ethyl ester, back flow reaction is continued 1 hour after being added dropwise to complete, add the ethylene glycol monomethyl ether solution of benzoyl peroxide the most in three times, every minor tick 1 hour, reaction 1 hour is continued after initiator solution adds for the third time.At this moment define main chain be with amido polar group side chain be acrylate based polymer there is the T-shaped or amphiphilic polymers of π type structure.This polymer has good dispersibility and dispersion stabilization to white carbon black.
Embodiment 3
In there is reflux condenser, agitator, the temperature display controller reactor with charging Dropping funnel, add the one-ended hydroxy polycaprolactone 20 grams that number-average molecular weight is 1000, and glycidyl fat, organotin catalysts, hydroquinone of polymerization retarder and the solvent butyl acetate of the hydroxyl value addition equimolar amounts according to resin, it is warming up to 150 DEG C and continues reaction 5 hours at such a temperature.After reaction terminates, add 5 grams of acrylic acid, 3 lauryl mercaptans, under agitation it is warming up to reflux temperature and continues backflow 1 hour at such a temperature, after backflow terminates, continue under stirring condition with reflux temperature, add, through Dropping funnel, the solution that a certain amount of azodiisobutyronitrile, butyl acetate and monomeric acrylic are formed in 3 hours, back flow reaction is continued 1 hour after being added dropwise to complete, add the propylene glycol monomethyl ether solution of azodiisobutyronitrile the most in three times, every minor tick 1 hour, continues reaction 1 hour after initiator solution adds for the third time.At this moment define main chain be with polar acidic group pendant be polycaprolactone type polymer there is the T-shaped or amphiphilic polymers of π type structure.This polymer has good dispersibility and dispersion stabilization to titanium dioxide.
Embodiment 4
In there is reflux condenser, agitator, the temperature display controller reactor with charging Dropping funnel, add the single-ended epoxy radicals base polypropylene glycol 20 grams that number-average molecular weight is 2000, and add the acrylic acid of equimolar amounts, a small amount of 4 bromide, hydroquinone of polymerization retarder and solvent butyl acetate according to the epoxide number of resin, it is warming up to 150 DEG C and continues reaction 5 hours at such a temperature.After reaction terminates, add 5 grams of acrylic acid, 3 lauryl mercaptans, under agitation it is warming up to reflux temperature and continues backflow 1 hour at such a temperature, after backflow terminates, continue under stirring condition with reflux temperature, add, through Dropping funnel, the solution that a certain amount of benzoyl peroxide, butyl acetate and monomeric acrylic are formed in 3 hours, back flow reaction is continued 1 hour after being added dropwise to complete, add the propylene glycol monomethyl ether solution of benzoyl peroxide the most in three times, every minor tick 1 hour, continues reaction 1 hour after initiator solution adds for the third time.At this moment define main chain be with polar acidic group pendant be polypropylene glycol type polymer there is the T-shaped or amphiphilic polymers of π type structure.This polymer has good dispersibility and dispersion stabilization to titanium dioxide.
Embodiment 5
In there is reflux condenser, agitator, the temperature display controller reactor with charging Dropping funnel, add the single-ended epoxy radicals base polypropylene glycol ether 20 grams that number-average molecular weight is 2000, and add the methacrylic acid of equimolar amounts, a small amount of 4 bromide, hydroquinone of polymerization retarder and solvent butyl acetate according to the epoxide number of resin, it is warming up to 150 degrees Celsius and continues reaction 5 hours at such a temperature.After reaction terminates, add a certain amount of 2 grams of acrylic acid and 3 grams of acrylic acid (N, N dimethyl amido) ethyl ester, 3 lauryl mercaptans, under agitation it is warming up to reflux temperature and continues to reflux 1 hour under counterflow condition at such a temperature, after backflow terminates, continue under stirring condition with reflux temperature, a certain amount of azodiisobutyronitrile is added through Dropping funnel in 3 hours, butyl acetate and monomeric acrylic and acrylic acid (N, N dimethyl amido) solution that formed of ethyl ester, back flow reaction is continued 1 hour after being added dropwise to complete, add the butyl glycol ether solution of azodiisobutyronitrile the most in three times, every minor tick 1 hour, reaction 1 hour is continued after initiator solution adds for the third time.At this moment define main chain be simultaneous with acid and basic polar groups side chain be polypropylene glycol type polymer there is the T-shaped or amphiphilic polymers of π type structure.This polymer has good dispersibility and dispersion stabilization to organic pigment.
Claims (8)
1. one kind has the T-shaped or amphiphilic polymers of π type structure, it is characterized in that: the molecular backbone of described amphiphilic polymers is the polyvinyl of the polar group with one or more, side chain is had the T-shaped or graft polymers of π type structure by what one or two oil loving polymer formed.
2. a synthetic method for the amphiphilic polymers with T-shaped or π type structure described in claim 1, is characterized in that:
1) in the presence of an organic by a kind of or two kinds carry out radical solution copolymerization reaction together containing the vinyl monomer of polar group, single-ended polyvinyl polymeric monomer, chain-transferring agent, polymeric reaction temperature is 80 ~ 170 DEG C, and the response time controlled at 3 ~ 15 hours；Course of reaction is gradually added radical polymerization initiator, the consumption of radical polymerization initiator is the 0.1% ~ 10% of vinyl monomer gross mass, the consumption of chain-transferring agent is the 0.1% ~ 10% of vinyl monomer gross mass, obtains described having the T-shaped or amphiphilic polymers solution of π type structure；
2) during the organic solvent used in polyreaction is benzene,toluene,xylene, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, butyl glycol ether, N-Methyl pyrrolidone any one or several, consumption of organic solvent is the 30% ~ 200% of vinyl monomer gross mass.
The synthetic method of the amphiphilic polymers with T-shaped or π type structure the most according to claim 2, it is characterized in that: the vinyl monomer containing polar group is acrylic acid, methacrylic acid, acrylamide, Methacrylamide, hydroethyl acrylate, β-hydroxy propyl acrylate, methacrylic acid β hydroxyl ethyl ester, methacrylic acid β hydroxypropyl acrylate, acrylic acid (N, N-dimethyl amido) ethyl ester, methacrylic acid (N, N-dimethyl amido) ethyl ester, more than one or more than one monomer in maleic anhydride, the number-average molecular weight of main chain controls within 500 to 2000.
The synthetic method of the amphiphilic polymers with T-shaped or π type structure the most according to claim 2, it is characterized in that: described single-ended polyvinyl is one-ended hydroxy polymer, single-ended carboxyl polymer, single-ended epoxy-based polymerization thing or single-ended amine based polymer and glycidyl acrylate, glycidyl methacrylate, hydroethyl acrylate, β-hydroxy propyl acrylate, methacrylic acid β hydroxyl ethyl ester, methacrylic acid β hydroxypropyl acrylate, 1-chloro-4-methyl-benzene, acrylic acid, a kind of monomer in methacrylic acid is formed by high molecular weight reactive, reaction is added total monomer weight 100,000/to the polymerization inhibitor of one thousandth amount；The number-average molecular weight of above-mentioned one-ended hydroxy polymer, single-ended carboxyl polymer, single-ended epoxy-based polymerization thing or single-ended amine based polymer all controls in the range of 500 to 3000.
The synthetic method of the amphiphilic polymers with T-shaped or π type structure the most according to claim 2, is characterized in that: described chain-transferring agent is lauryl mercaptan, n-butyl mercaptan, 3-isooctyl mercaptopropionate or TPMS.
The synthetic method of the amphiphilic polymers with T-shaped or π type structure the most according to claim 2, is characterized in that: described radical polymerization initiator is initiator or the per-compound type initiator of azo-type.
The synthetic method of the amphiphilic polymers with T-shaped or π type structure the most according to claim 6, is characterized in that: described azo-type initiator is azodiisobutyronitrile, 2,2'-Azobis(2,4-dimethylvaleronitrile) or 4,4'-azo (4-cyanopentanoic acid).
The synthetic method of the amphiphilic polymers with T-shaped or π type structure the most according to claim 2, is characterized in that: described per-compound type initiator is dibenzoyl peroxide, dilauroyl peroxide, cyclohexanone peroxide, isopropyl benzene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, the benzoyl peroxide tert-butyl ester, the peroxidating trimethylacetic acid tert-butyl ester, t-amyl peroxy hydrogen, two tertiary amyl peroxide, 1.1-(di-tert-butyl peroxide) thiacyclohexane or the peroxidating pivalic acid tert-butyl ester.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109233664A (en) * | 2018-06-12 | 2019-01-18 | 哈尔滨工业大学无锡新材料研究院 | A kind of UV curing type adhesive, preparation method and application |
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| US6117921A (en) * | 1996-08-30 | 2000-09-12 | E. I. Du Pont De Nemours And Company | Process for making printed images using pigmented ink jet compositions |
| JP2001354516A (en) * | 1996-06-28 | 2001-12-25 | L'oreal Sa | Copolymer grafted with hydrophobic macromonomer |
| CN103570887A (en) * | 2013-10-29 | 2014-02-12 | 中国石油化工股份有限公司 | Amphiphilic block T-shaped copolymer and preparation method thereof |
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2016
- 2016-05-16 CN CN201610317856.0A patent/CN105924597A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001354516A (en) * | 1996-06-28 | 2001-12-25 | L'oreal Sa | Copolymer grafted with hydrophobic macromonomer |
| US6117921A (en) * | 1996-08-30 | 2000-09-12 | E. I. Du Pont De Nemours And Company | Process for making printed images using pigmented ink jet compositions |
| CN103570887A (en) * | 2013-10-29 | 2014-02-12 | 中国石油化工股份有限公司 | Amphiphilic block T-shaped copolymer and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| JIANQUAN TAN ET AL: "Preparation and properties of UV-curable waterborne comb-like (meth)acrylate copolymers with long fluorinated side chains", 《PROGRESS IN ORGANIC COATINGS》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109233664A (en) * | 2018-06-12 | 2019-01-18 | 哈尔滨工业大学无锡新材料研究院 | A kind of UV curing type adhesive, preparation method and application |
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Application publication date: 20160907 |