CN103319640A - Preparation method of styrene-acrylic resin with high solid content - Google Patents
Preparation method of styrene-acrylic resin with high solid content Download PDFInfo
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- CN103319640A CN103319640A CN2013102277071A CN201310227707A CN103319640A CN 103319640 A CN103319640 A CN 103319640A CN 2013102277071 A CN2013102277071 A CN 2013102277071A CN 201310227707 A CN201310227707 A CN 201310227707A CN 103319640 A CN103319640 A CN 103319640A
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Abstract
The present invention relates to a preparation method of styrene-acrylic resin with high solid content, which belongs to the field of functional polymer. The preparation method comprises the following steps: mixing comonomer, functional monomer and an initiator evenly and drop-wise adding the mixture into a solution at the temperature of 130 DEG C to 140 DEG C, to obtain styrene-acrylic resin after conventional free radical polymerization reaction for six to eight hours. The method provided by the invention is able to introduce a novel compound containing polymerizable double bond and chain transfer hydrosulphonyl into a reaction system, generating a co-polymer with branched structure in situ. Under the condition of the same molecular weight, the viscosity of the branched co-polymer is lower than that of the linear co-polymer; the mass ratio of the novel compound containing polymerizable double bond and chain transfer hydrosulphonyl to alpha methyl styrene linear dipolymer is adjusted; the styrene-acrylic resin with relatively low viscosity and high solid content can be obtained by adjusting the branching degree and molecular weight of the reaction copolymer.
Description
Technical field
The present invention relates to a kind of preparation method of highly filled styrene-acrylic resin, belong to the applied technical field of branched polymer in the Polymer Synthesizing.
Background technology
Cinnamic acrylic ester class interpolymer (styrene-acrylic resin) has preferably chemical resistance, and higher hardness and the lower advantages such as production cost are widely used in paint, building coating field.The method for preparing at present styrene-acrylic resin mainly is divided into two classes: solution polymerization and letex polymerization.No matter be the styrene-acrylic resin of solution polymerization or letex polymerization preparation, its solids content and viscosity all are important indicators, and it is directly connected to consumption, production energy consumption and the solvent recuperation cost of solvent, that is to say directly production cost is played decisive role.But, the styrene-acrylic resin of at present solution polymerization and letex polymerization preparation, its solids content is 30%～60%.After solid content surpasses 60%, the solid content of every increase one percentage point, the system viscosity can sharply increase, and auto-acceleration effect is more violent in the reaction process, but therefore is difficult to obtain highly filled paint and the coating of stable performance and normal construction.
If obtain highly filled resin, just must regulate its viscosity.Generally speaking, the viscosity of the polymkeric substance that radical polymerization obtains own is very high, can reduce viscosity by the molecular weight that reduces polymkeric substance, but, reduce simply molecular weight, can cause the hydroxyl value on each molecular resin inadequate, cause the back crosslinking curing incomplete, molecular weight reduces so that the second-order transition temperature of resin reduces simultaneously, directly has influence on resin property, finally has influence on the performance of paint and coating.
Branched polymer is because the three-dimensional ball-like structure of its uniqueness, the characteristics such as intermolecular difficult generation chain entanglement, and than simple linear polymer, it has lower melting viscosity and solution viscosity, hole and good solubility energy in a large amount of molecules.Therefore introduce side chain at resin structure, can effectively reduce the viscosity of resin, thus the solids content of raising paint or coating, and the consumption of minimizing solvent reduces solvent recuperation cost and improvement to the impact of environment.
The present invention shifts the novel cpd of sulfydryl and alpha-methyl styrene linear dimerization body as function monomer to contain polymerizable double bond and chain, utilize two keys and sulfydryl in the novel cpd to form the polymkeric substance with branched structure, utilize simultaneously sulfydryl and alpha-methyl styrene linear dimerization body to regulate the molecular weight of resin, obtain the lower interpolymer of viscosity, thereby obtain highly filled styrene-acrylic resin.This invention is significant with application to the theoretical investigation of highly filled paint and coating.
Summary of the invention
The invention discloses a kind of preparation method of highly filled styrene-acrylic resin, it is characterized in that: the novel cpd that will contain polymerizable double bond and chain transfer sulfydryl is incorporated in the reaction system, and original position generates the interpolymer with branched structure; Adjusting contains polymerizable double bond and chain and shifts the novel cpd of sulfydryl and the mass ratio of alpha-methyl styrene linear dimerization body, and degree of branching and molecular weight that can the conditioned reaction multipolymer obtain viscosity relatively low, the styrene-acrylic resin that solids content is high.Operation is simple for this polyreaction, improves the solids content of styrene-acrylic resin, can reduce the consumption of solvent and the impact that production process is brought environment.
A kind of preparation method of highly filled styrene-acrylic resin, carry out according to following step: be added drop-wise to temperature after comonomer, function monomer and initiator are evenly mixed and be in 130～140 ℃ the solvent, through conventional Raolical polymerizable 6～8 hours, obtain styrene-acrylic resin.
Wherein the mass ratio of comonomer, function monomer, initiator, solvent is:
Comonomer: function monomer: initiator: solvent=(64～69): (0.95～3): (0.05～3): 30
Wherein said function monomer is that polymerizable double bond and chain shift the novel cpd of sulfydryl and the mixture of alpha-methyl styrene linear dimerization body, and both mass ratioes are 0～3:1; The mixture time for adding is 4 hours.
Wherein said comonomer is one or several in vinylbenzene, methyl methacrylate, butyl acrylate, Propylene glycol monoacrylate or the Isooctyl acrylate monomer.
Wherein said initiator is the initiator of the radical polymerizations such as benzoyl peroxide.
Wherein said solvent is dimethylbenzene, heavy aromatics or 1-Methoxy-2-propyl acetate.
Advantage of the present invention: the novel cpd that will contain polymerizable double bond and chain transfer sulfydryl is incorporated in the reaction system, and original position generates the interpolymer with branched structure; Recycling sulfydryl and alpha-methyl styrene linear dimerization body are regulated the molecular weight of resin; Adjusting contains polymerizable double bond and chain shifts the novel cpd of sulfydryl and the mass ratio of alpha-methyl styrene linear dimerization body, degree of branching and molecular weight that can the conditioned reaction multipolymer, obtain the lower interpolymer of viscosity, thereby obtain highly filled styrene-acrylic resin.Operation is simple, low production cost, and environmental pollution reduces.
Description of drawings
The limiting viscosity of Fig. 1 embodiment 1,2,6 and 7 resulting polymers is with the change curve (Mark-Houwink curve) of molecular weight.
Fig. 2 is branching factor g ' and the change of molecular weight trend map (g ' be limiting viscosity (Intrinsic Viscosity) ratio g '=[η] of branched polymer under the same molecular amount and simple linear polymer of embodiment 1 and 2 gained branched polymers
Branched/ [η]
LinearG ' is less, and degree of branching is higher).
Embodiment
With monomer styrene (5.2365g, 0.05mol), methyl methacrylate (5.1993g, 0.052mol), n-butyl acrylate (7.4008g, 0.057mol), Isooctyl acrylate monomer (3.6563g, 0.020mol), Propylene glycol monoacrylate (9.0095g, 0.069mol), function monomer dimer (0.4123g), initiator B PO(0.5124g, 2mmol) mix after, be added drop-wise to temperature and be 135 ℃ solvent xylene (7.6874g), in 1-Methoxy-2-propyl acetate (2.7048g) and the heavy aromatics (2.7105g), system back flow reaction 4 hours, mixture dropwises.Constant temperature continues reaction 3 hours, and reaction stops, and obtains water white resin.Recording resin solid content and be 70.22%, Ge Shi pipe, to record its viscosity be 140.9s.Adopt three detection gel permeation chromatographs that polymkeric substance is analyzed, the result is as follows: scattering of light weight-average molecular weight M
W.MALLS=22260, molecular weight distribution PDI=2.0.Fig. 1 is that the limiting viscosity of this polymkeric substance is with the change curve (Mark-Houwink curve) of molecular weight.Do not add function monomer methacrylic acid-3-sulfydryl propionyloxy ethyl ester among this embodiment, the polymkeric substance that obtains is simple linear polymer.Provide the corresponding limiting viscosity of this embodiment among Fig. 1, its purpose is used for comparing with the limiting viscosity of branched polymer, thereby judges whether formed polymkeric substance is the polymkeric substance of branched structure.
Embodiment 2
With monomer styrene (5.2146g, 0.05mol), methyl methacrylate (5.2017g, 0.052mol), n-butyl acrylate (10.4662g, 0.081mol), Propylene glycol monoacrylate (9.0020g, 0.069mol), function monomer methacrylic acid-3-sulfydryl propionyloxy ethyl ester (0.2256g, 0.52mmol) and dimer (0.1864g), initiator B PO(0.0230g, 0.09mmol) mix after, be added drop-wise to temperature and be 135 ℃ solvent xylene (7.6795g), in 1-Methoxy-2-propyl acetate (2.6872g) and the heavy aromatics (2.6898g), system back flow reaction 4 hours, mixture dropwises.Constant temperature continues reaction 3 hours, and reaction stops, and obtains the transparent resin of little Huang.Recording resin solid content and be 68.51%, Ge Shi pipe, to record its viscosity be 131.3s.Adopt three detection gel permeation chromatographs that polymkeric substance is analyzed, the result is as follows: scattering of light weight-average molecular weight M
W.MALLS=122300, molecular weight distribution PDI=2.9, g '=0.61.Fig. 1 be the limiting viscosity of this polymkeric substance with the change curve (Mark-Houwink curve) of molecular weight, Fig. 2 is that this polymkeric substance branching factor is along with the change curve of molecular weight.The limiting viscosity that provides this polymkeric substance among Fig. 1 with compare littlely with the limiting viscosity of molecular weight simple linear polymer, illustrate that the polymkeric substance that this embodiment forms is branched polymer.The polymkeric substance that Fig. 2 further specifies formation is branched polymer.The weight-average molecular weight M of this embodiment resulting polymers
W.MALLSThe weight-average molecular weight M of resulting polymers among=122300, the embodiment 1
W.MALLS=22600, but both solution viscosities (the Ge Shi pipe is surveyed) are close, and the reason that forms this result is exactly because the polymkeric substance of embodiment 2 gained is branched polymer.Therefore, the successful preparation of branching styrene-acrylic resin is for the preparation of highly filled styrene-acrylic resin provides direct method.Regulate molecular weight and the degree of branching of branching styrene-acrylic resin, can regulate the viscosity of styrene-acrylic resin, thereby regulate the solids content of styrene-acrylic resin.
Embodiment 3
With monomer styrene (5.1993g, 0.05mol), methyl methacrylate (5.2088g, 0.052mol), n-butyl acrylate (9.4562g, 0.073mol) and Propylene glycol monoacrylate (8.0192g, 0.062mol), function monomer methacrylic acid-3-sulfydryl propionyloxy ethyl ester (0.6363g, 1.46mmol) and dimer (0.6782g), initiator B PO(1.3090g, 0.005mol) mix after, be added drop-wise to temperature and be 135 ℃ solvent xylene (7.6843g), in 1-Methoxy-2-propyl acetate (2.6903g) and the heavy aromatics (2.6924g), system back flow reaction 4 hours, mixture dropwises.Constant temperature continues reaction 3 hours, and reaction stops, and obtains the transparent resin of little Huang.Recording resin solid content and be 69.32%, Ge Shi pipe, to record its viscosity be 64.5s.Adopt three detection gel permeation chromatographs that polymkeric substance is analyzed, the result is as follows: scattering of light weight-average molecular weight M
W.MALLS=16700, molecular weight distribution PDI=2.3, g '=0.71.Fig. 1 be the limiting viscosity of this polymkeric substance with the change curve (Mark-Houwink curve) of molecular weight, Fig. 2 is that this polymkeric substance branching factor is along with the change curve of molecular weight.The limiting viscosity that provides this polymkeric substance among Fig. 1 with compare littlely with the limiting viscosity of molecular weight simple linear polymer, illustrate that the polymkeric substance that this embodiment forms is branched polymer.The polymkeric substance that Fig. 2 further specifies formation is branched polymer.
Embodiment 4
With monomer styrene (52.0048g, 0.5mol), methyl methacrylate (52.0114g, 0.52mol), n-butyl acrylate (74.0128g, 0.57mol), Isooctyl acrylate monomer (36.5114g, 0.2mol) and Propylene glycol monoacrylate (90.0120g, 0.69mol), function monomer methacrylic acid-3-sulfydryl propionyloxy ethyl ester (1.3858g, 3.18mmol) and dimer (3.0495g), initiator B PO(13.0190g, 0.05mol) mix after, be added drop-wise to temperature and be 135 ℃ solvent xylene (76.8207g), in 1-Methoxy-2-propyl acetate (26.9890g) and the heavy aromatics (26.9140g), system back flow reaction 4 hours, mixture dropwises.Constant temperature continues reaction 3 hours, and reaction stops, and obtains the transparent resin of little Huang.Recording resin solid content and be 70.73%, Ge Shi pipe, to record its viscosity be 80.1s.Adopt three detection gel permeation chromatographs that polymkeric substance is analyzed, the result is as follows: scattering of light weight-average molecular weight M
W.MALLS=16040, molecular weight distribution PDI=1.9, g '=0.73.Fig. 1 is that the limiting viscosity of this polymkeric substance is with the change curve (Mark-Houwink curve) of molecular weight.
Embodiment 5
With monomer styrene (5.2095g, 0.05mol), methyl methacrylate (5.2082g, 0.052mol), n-butyl acrylate (7.1180g, 0.057mol), Isooctyl acrylate monomer (3.6624g, 0.020mol) and Propylene glycol monoacrylate (9.0143g, 0.069mol), function monomer methacrylic acid-3-sulfydryl propionyloxy ethyl ester (0.7691g, 1.76mmol) and dimer (0.3029g), initiator B PO(1.3085g, 0.005mol) mix after, be added drop-wise to temperature and be 135 ℃ solvent xylene (7.6828g), in 1-Methoxy-2-propyl acetate (2.7029g) and the heavy aromatics (2.6948g), system back flow reaction 4 hours, mixture dropwises.Constant temperature continues reaction 2 hours, and reaction stops, and obtains the transparent resin of little Huang.Recording resin solid content and be 68.76%, Ge Shi pipe, to record its viscosity be 64.6s.Adopt three detection gel permeation chromatographs that polymkeric substance is analyzed, the result is as follows: scattering of light weight-average molecular weight M
W.MALLS=27460, molecular weight distribution PDI=2.7, g '=0.76.
Embodiment 6
With monomer styrene (5.2041g, 0.05mol), methyl methacrylate (5.2145g, 0.052mol), n-butyl acrylate (7.1095g, 0.055mol), Isooctyl acrylate monomer (3.3556g, 0.018mol) and Propylene glycol monoacrylate (9.0143g, 0.069mol), function monomer methacrylic acid-3-sulfydryl propionyloxy ethyl ester (0.2792g, 0.64mmol) and dimer (0.3073g), initiator B PO(1.3104g, 0.005mol) mix after, be added drop-wise to temperature and be in 140 ℃ the solvent xylene (7.6793g) and 1-Methoxy-2-propyl acetate (5.3946g), system back flow reaction 4 hours, mixture dropwises.Constant temperature continues reaction 3 hours, and reaction stops, and obtains the transparent resin of little Huang.Recording resin solid content and be 64.16%, Ge Shi pipe, to record its viscosity be 53.6s.Adopt three detection gel permeation chromatographs that polymkeric substance is analyzed, the result is as follows: scattering of light weight-average molecular weight M
W.MALLS=28990, molecular weight distribution PDI=2.5, g '=0.71.
Embodiment 7
With monomer styrene (5.1997g, 0.05mol), methyl methacrylate (5.2050g, 0.052mol), n-butyl acrylate (7.4045g, 0.057mol), Isooctyl acrylate monomer (3.3572g, 0.019mol) and Propylene glycol monoacrylate (9.0062g, 0.069mol), function monomer methacrylic acid-3-sulfydryl propionyloxy ethyl ester (0.1344g, 0.32mmol) and dimer (0.3988g), initiator B PO(1.3099g, 0.005mol) mix after, be added drop-wise to temperature and be in 130 ℃ the solvent xylene (7.6793g) and 1-Methoxy-2-propyl acetate (5.3946g), system back flow reaction 4 hours, mixture dropwises.Constant temperature continues reaction 3 hours, and reaction stops, and obtains the transparent resin of little Huang.Recording resin solid content and be 69.69%, Ge Shi pipe, to record its viscosity be 99.8s.Adopt three detection gel permeation chromatographs that polymkeric substance is analyzed, the result is as follows: scattering of light weight-average molecular weight M
W.MALLS=22680, molecular weight distribution PDI=2.3, g '=0.88.
Claims (5)
1. the preparation method of a highly filled styrene-acrylic resin, it is characterized in that carrying out according to following step: be added drop-wise to temperature after comonomer, function monomer and initiator are evenly mixed and be in 130 ~ 140 ℃ the solvent, through conventional Raolical polymerizable 6 ~ 8 hours, obtain styrene-acrylic resin; Wherein the mass ratio of comonomer, function monomer, initiator, solvent is:
Comonomer: function monomer: initiator: solvent=(64 ~ 69): (0.95 ~ 3): (0.05 ~ 3): 30.
2. the preparation method of a kind of highly filled styrene-acrylic resin according to claim 1, it is characterized in that wherein said function monomer is that polymerizable double bond and chain shift the novel cpd of sulfydryl and the mixture of vinyl toluene linear dimerization body, both mass ratioes are 0 ~ 3:1; The mixture time for adding is 4 hours.
3. the preparation method of a kind of highly filled styrene-acrylic resin according to claim 1 is characterized in that wherein said comonomer is one or several in vinylbenzene, methyl methacrylate, butyl acrylate, Propylene glycol monoacrylate or the Isooctyl acrylate monomer.
4. the preparation method of a kind of highly filled styrene-acrylic resin according to claim 1 is characterized in that wherein said initiator is the initiator of the radical polymerizations such as benzoyl peroxide.
5. the preparation method of a kind of highly filled styrene-acrylic resin according to claim 1 is characterized in that wherein said solvent is dimethylbenzene, heavy aromatics or 1-Methoxy-2-propyl acetate.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004224840A (en) * | 2003-01-20 | 2004-08-12 | Sakai Chem Ind Co Ltd | Chain transfer agent for styrene-acrylic polymer polymerization, method for producing resin for polymer toner and resin used for polymer toner and obtained thereby |
| CN101575397A (en) * | 2009-06-02 | 2009-11-11 | 中山大学 | Method for preparing water-soluble solid styrene/acrylic resin and application thereof |
| CN101787097A (en) * | 2010-03-12 | 2010-07-28 | 北京化工大学 | Preparation method of water-soluble solid styrene-acrylic resin |
| CN102936305A (en) * | 2012-10-30 | 2013-02-20 | 常州大学 | Method for preparing branched polymer through suspension polymerization |
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- 2013-06-07 CN CN201310227707.1A patent/CN103319640B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004224840A (en) * | 2003-01-20 | 2004-08-12 | Sakai Chem Ind Co Ltd | Chain transfer agent for styrene-acrylic polymer polymerization, method for producing resin for polymer toner and resin used for polymer toner and obtained thereby |
| CN101575397A (en) * | 2009-06-02 | 2009-11-11 | 中山大学 | Method for preparing water-soluble solid styrene/acrylic resin and application thereof |
| CN101787097A (en) * | 2010-03-12 | 2010-07-28 | 北京化工大学 | Preparation method of water-soluble solid styrene-acrylic resin |
| CN102936305A (en) * | 2012-10-30 | 2013-02-20 | 常州大学 | Method for preparing branched polymer through suspension polymerization |
Non-Patent Citations (1)
| Title |
|---|
| 李斐等: "常规自由基聚合法合成支化聚（丙烯腈-醋酸乙烯酯）", 《高分子材料科学与工程》 * |
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