CN103319640B - A kind of preparation method of styrene-acrylic resin with high solid content - Google Patents
A kind of preparation method of styrene-acrylic resin with high solid content Download PDFInfo
- Publication number
- CN103319640B CN103319640B CN201310227707.1A CN201310227707A CN103319640B CN 103319640 B CN103319640 B CN 103319640B CN 201310227707 A CN201310227707 A CN 201310227707A CN 103319640 B CN103319640 B CN 103319640B
- Authority
- CN
- China
- Prior art keywords
- styrene
- molecular weight
- acrylic resin
- solid content
- viscosity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The preparation method of a kind of styrene-acrylic resin with high solid content of the present invention, belongs to the field of functional polymer.Carrying out according to following step: be in the solvent of 130 ~ 140 DEG C by being added drop-wise to temperature after comonomer, function monomer and initiator Homogeneous phase mixing, through conventional Raolical polymerizable 6 ~ 8 hours, obtaining styrene-acrylic resin.Novel cpd containing polymerizable double bond and chain tra nsfer sulfydryl is incorporated in reaction system by the present invention, and in-situ preparation has the interpolymer of branched structure, and under same molecular weight condition, this branched interpolymer is lower than line style interpolymer viscosity; Regulate containing polymerizable double bond and the novel cpd of chain tra nsfer sulfydryl and the mass ratio of vinyl toluene linear dimerization body, degree of branching and the molecular weight of reaction multipolymer can be regulated, obtain viscosity relatively low, the styrene-acrylic resin that solids content is high.
Description
Technical field
The present invention relates to a kind of preparation method of styrene-acrylic resin with high solid content, belong to the applied technical field of branched polymer in Polymer Synthesizing.
Background technology
Cinnamic acrylic ester class interpolymer (styrene-acrylic resin) has good chemical resistance, and the advantages such as higher hardness and lower production cost, are widely used in paint, building coating field.The method preparing styrene-acrylic resin at present is mainly divided into two classes: solution polymerization and letex polymerization.No matter be styrene-acrylic resin prepared by solution polymerization or letex polymerization, its solids content and viscosity are all important indicators, and it is directly connected to the consumption of solvent, production energy consumption and solvent recuperation cost, that is directly play decisive role to production cost.But styrene-acrylic resin prepared by current solution polymerization and letex polymerization, its solids content is 30% ~ 60%.After solid content is more than 60%, often increase the solid content of one percentage point, system viscosity can sharply increase, and in reaction process, auto-acceleration effect is more violent, is therefore difficult to obtain stable performance and can the highly filled paint of normal construction and coating.
To obtain highly filled resin, just must regulate its viscosity.Generally, the viscosity of the polymkeric substance that radical polymerization obtains own is very high, molecular weight by reducing polymkeric substance reduces viscosity, but, reduce molecular weight simply, the hydroxyl value on each molecular resin can be caused inadequate, cause crosslinking curing below incomplete, molecular weight reduction simultaneously makes the second-order transition temperature of resin reduce, and directly has influence on resin property, finally has influence on the performance of paint and coating.
Branched polymer is due to the three-dimensional globular structure of its uniqueness, and the features such as intermolecular not easily generation chain entanglement, compared to simple linear polymer, it has lower melting viscosity and solution viscosity, hole and good solubility energy in a large amount of molecules.Therefore on resin structure, introduce side chain, effectively can reduce the viscosity of resin, thus improve the solids content of paint or coating, reduce the consumption of solvent, the impact reducing solvent recuperation cost and improve environment.
The present invention with the novel cpd containing polymerizable double bond and chain tra nsfer sulfydryl and alpha-methyl styrene linear dimerization body for function monomer, the double bond in novel cpd and sulfydryl is utilized to form the polymkeric substance with branched structure, utilize sulfydryl and alpha-methyl styrene linear dimerization body to regulate the molecular weight of resin simultaneously, obtain the interpolymer that viscosity is lower, thus obtain styrene-acrylic resin with high solid content.The theoretical investigation of this invention to highly filled paint and coating is significant with application.
Summary of the invention
The invention discloses a kind of preparation method of styrene-acrylic resin with high solid content, it is characterized in that: be incorporated in reaction system by the novel cpd containing polymerizable double bond and chain tra nsfer sulfydryl, in-situ preparation has the interpolymer of branched structure; Regulate containing polymerizable double bond and the novel cpd of chain tra nsfer sulfydryl and the mass ratio of alpha-methyl styrene linear dimerization body, degree of branching and the molecular weight of reaction multipolymer can be regulated, 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 impact that the consumption of solvent and production process are brought environment.
A kind of preparation method of styrene-acrylic resin with high solid content, carry out according to following step: be in the solvent of 130 ~ 140 DEG C by being added drop-wise to temperature after comonomer, function monomer and initiator Homogeneous phase mixing, 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 the novel cpd of polymerizable double bond and chain tra nsfer sulfydryl and the mixture of alpha-methyl styrene linear dimerization body, and both mass ratioes are 0 ~ 3:1; Mixture time for adding is 4 hours.
Wherein said comonomer is one or several in vinylbenzene, methyl methacrylate, butyl acrylate, Propylene glycol monoacrylate or 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: be incorporated in reaction system by the novel cpd containing polymerizable double bond and chain tra nsfer sulfydryl, in-situ preparation has the interpolymer of branched structure; Recycling sulfydryl and alpha-methyl styrene linear dimerization body regulate the molecular weight of resin; Regulate containing polymerizable double bond and the novel cpd of chain tra nsfer sulfydryl and the mass ratio of alpha-methyl styrene linear dimerization body, degree of branching and the molecular weight of reaction multipolymer can be regulated, obtain the interpolymer that viscosity is lower, thus obtain styrene-acrylic resin with high solid content.Operation is simple, low production cost, and environmental pollution reduces.
Accompanying drawing explanation
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 (IntrinsicViscosity) ratio g '=[η] of branched polymer and simple linear polymer under same molecular amount of embodiment 1 and 2 gained branched polymer
branched/ [η]
linear; G ' is less, and degree of branching is higher).
Embodiment
Embodiment 1
By 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, after 2mmol) mixing, be added drop-wise to the solvent xylene (7.6874g) that temperature is 135 DEG C, in 1-Methoxy-2-propyl acetate (2.7048g) and 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 is 70.22%, and it is 140.9s that grignard pipe records its viscosity.Adopt three to detect gel permeation chromatograph to analyze polymkeric substance, result is as follows: scattering of light weight-average molecular weight M
w.MALLS=22260, molecular weight distribution PDI=2.0.Fig. 1 is the change curve (Mark-Houwink curve) of limiting viscosity with molecular weight of this polymkeric substance.Do not add function monomer methacrylic acid-3-mercaptopropionyl oxygen base ethyl ester in this embodiment, the polymkeric substance obtained is simple linear polymer.Provide the limiting viscosity corresponding to this embodiment in Fig. 1, its object is used for comparing with the limiting viscosity of branched polymer, thus judges that whether formed polymkeric substance is the polymkeric substance of branched structure.
Embodiment 2
By 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-mercaptopropionyl oxygen base ethyl ester (0.2256g, 0.52mmol) with dimer (0.1864g), initiator B PO(0.0230g, after 0.09mmol) mixing, be added drop-wise to the solvent xylene (7.6795g) that temperature is 135 DEG C, in 1-Methoxy-2-propyl acetate (2.6872g) and heavy aromatics (2.6898g), system back flow reaction 4 hours, mixture dropwises.Constant temperature continues reaction 3 hours, and reaction stops, and obtains the resin that micro-Huang is transparent.Recording resin solid content is 68.51%, and it is 131.3s that grignard pipe records its viscosity.Adopt three to detect gel permeation chromatograph to analyze polymkeric substance, 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 is the change curve (Mark-Houwink curve) of limiting viscosity with molecular weight of this polymkeric substance, and Fig. 2 is the change curve of this polymer branching factor along with molecular weight.The limiting viscosity providing this polymkeric substance in Fig. 1 is little compared with the limiting viscosity of same molecular weight linear polymer, illustrates that the polymkeric substance that this embodiment is formed is branched polymer.The polymkeric substance that Fig. 2 further illustrates formation is branched polymer.The weight-average molecular weight M of this embodiment resulting polymers
w.MALLS=122300, the weight-average molecular weight M of resulting polymers in embodiment 1
w.MALLS=22600, but both solution viscosities (grignard pipe surveyed) are close, and the reason forming this result is exactly because the polymkeric substance of embodiment 2 gained is branched polymer.Therefore, the successful preparation of branching styrene-acrylic resin, the preparation for styrene-acrylic resin with high solid content provides direct method.Regulate molecular weight and the degree of branching of branching styrene-acrylic resin, the viscosity of styrene-acrylic resin can be regulated, thus regulate the solids content of styrene-acrylic resin.
Embodiment 3
By monomer styrene (5.1993g, 0.05mol), methyl methacrylate (5.2088g, 0.052mol), n-butyl acrylate (9.4562g, 0.073mol) with Propylene glycol monoacrylate (8.0192g, 0.062mol), function monomer methacrylic acid-3-mercaptopropionyl oxygen base ethyl ester (0.6363g, 1.46mmol) with dimer (0.6782g), initiator B PO(1.3090g, after 0.005mol) mixing, be added drop-wise to the solvent xylene (7.6843g) that temperature is 135 DEG C, in 1-Methoxy-2-propyl acetate (2.6903g) and heavy aromatics (2.6924g), system back flow reaction 4 hours, mixture dropwises.Constant temperature continues reaction 3 hours, and reaction stops, and obtains the resin that micro-Huang is transparent.Recording resin solid content is 69.32%, and it is 64.5s that grignard pipe records its viscosity.Adopt three to detect gel permeation chromatograph to analyze polymkeric substance, 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 is the change curve (Mark-Houwink curve) of limiting viscosity with molecular weight of this polymkeric substance, and Fig. 2 is the change curve of this polymer branching factor along with molecular weight.The limiting viscosity providing this polymkeric substance in Fig. 1 is little compared with the limiting viscosity of same molecular weight linear polymer, illustrates that the polymkeric substance that this embodiment is formed is branched polymer.The polymkeric substance that Fig. 2 further illustrates formation is branched polymer.
Embodiment 4
By 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) with Propylene glycol monoacrylate (90.0120g, 0.69mol), function monomer methacrylic acid-3-mercaptopropionyl oxygen base ethyl ester (1.3858g, 3.18mmol) with dimer (3.0495g), initiator B PO(13.0190g, after 0.05mol) mixing, be added drop-wise to the solvent xylene (76.8207g) that temperature is 135 DEG C, in 1-Methoxy-2-propyl acetate (26.9890g) and heavy aromatics (26.9140g), system back flow reaction 4 hours, mixture dropwises.Constant temperature continues reaction 3 hours, and reaction stops, and obtains the resin that micro-Huang is transparent.Recording resin solid content is 70.73%, and it is 80.1s that grignard pipe records its viscosity.Adopt three to detect gel permeation chromatograph to analyze polymkeric substance, 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 the change curve (Mark-Houwink curve) of limiting viscosity with molecular weight of this polymkeric substance.
Embodiment 5
By 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) with Propylene glycol monoacrylate (9.0143g, 0.069mol), function monomer methacrylic acid-3-mercaptopropionyl oxygen base ethyl ester (0.7691g, 1.76mmol) with dimer (0.3029g), initiator B PO(1.3085g, after 0.005mol) mixing, be added drop-wise to the solvent xylene (7.6828g) that temperature is 135 DEG C, in 1-Methoxy-2-propyl acetate (2.7029g) and heavy aromatics (2.6948g), system back flow reaction 4 hours, mixture dropwises.Constant temperature continues reaction 2 hours, and reaction stops, and obtains the resin that micro-Huang is transparent.Recording resin solid content is 68.76%, and it is 64.6s that grignard pipe records its viscosity.Adopt three to detect gel permeation chromatograph to analyze polymkeric substance, 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
By 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) with Propylene glycol monoacrylate (9.0143g, 0.069mol), function monomer methacrylic acid-3-mercaptopropionyl oxygen base ethyl ester (0.2792g, 0.64mmol) with dimer (0.3073g), initiator B PO(1.3104g, after 0.005mol) mixing, being added drop-wise to temperature is in the solvent xylene (7.6793g) of 140 DEG C 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 resin that micro-Huang is transparent.Recording resin solid content is 64.16%, and it is 53.6s that grignard pipe records its viscosity.Adopt three to detect gel permeation chromatograph to analyze polymkeric substance, 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
By 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) with Propylene glycol monoacrylate (9.0062g, 0.069mol), function monomer methacrylic acid-3-mercaptopropionyl oxygen base ethyl ester (0.1344g, 0.32mmol) with dimer (0.3988g), initiator B PO(1.3099g, after 0.005mol) mixing, being added drop-wise to temperature is in the solvent xylene (7.6793g) of 130 DEG C 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 resin that micro-Huang is transparent.Recording resin solid content is 69.69%, and it is 99.8s that grignard pipe records its viscosity.Adopt three to detect gel permeation chromatograph to analyze polymkeric substance, 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 (1)
1. the preparation method of a styrene-acrylic resin with high solid content, it is characterized in that carrying out according to following step: by monomer styrene 0.5mol, methyl methacrylate 0.52mol, n-butyl acrylate 0.57mol, Isooctyl acrylate monomer 0.2mol and Propylene glycol monoacrylate 0.69mol, function monomer methacrylic acid-3-mercaptopropionyl oxygen base ethyl ester 3.18mmol and dimer 3.0495g, initiator B PO, after 0.05mol mixes, be added drop-wise to the solvent xylene 76.8207g that temperature is 135 DEG C, in 1-Methoxy-2-propyl acetate 26.9890g and heavy aromatics 26.9140g, system back flow reaction 4 hours, mixture dropwises, constant temperature continues reaction 3 hours, and reaction stops, and obtains the resin that micro-Huang is transparent, recording resin solid content is 70.73%, and it is 80.1s that grignard pipe records its viscosity, adopt three to detect gel permeation chromatograph to analyze polymkeric substance, result is as follows: scattering of light weight-average molecular weight
m w.MALLS=16040, molecular weight distribution PDI=1.9,
g'=0.73.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310227707.1A CN103319640B (en) | 2013-06-07 | 2013-06-07 | A kind of preparation method of styrene-acrylic resin with high solid content |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310227707.1A CN103319640B (en) | 2013-06-07 | 2013-06-07 | A kind of preparation method of styrene-acrylic resin with high solid content |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103319640A CN103319640A (en) | 2013-09-25 |
| CN103319640B true CN103319640B (en) | 2015-12-23 |
Family
ID=49188720
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310227707.1A Active CN103319640B (en) | 2013-06-07 | 2013-06-07 | A kind of preparation method of styrene-acrylic resin with high solid content |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103319640B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (1)
| 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 |
-
2013
- 2013-06-07 CN CN201310227707.1A patent/CN103319640B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
|---|
| 常规自由基聚合法合成支化聚（丙烯腈-醋酸乙烯酯）;李斐等;《高分子材料科学与工程》;20121231;第28卷(第12期);第29-31,36页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103319640A (en) | 2013-09-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103936913B (en) | For thickener, its preparation method of self-compacting concrete and apply the self-compacting concrete of this thickener | |
| CN103320112B (en) | A kind of anti-shearing dendritic polymers oil-displacing agent and synthetic method thereof | |
| CN104327213B (en) | A kind of high wax viscous crude nano composite material pour point depressant and preparation method thereof | |
| CN102702420B (en) | Preparation method of color polyacrylate polymer microspheres | |
| CN102382241A (en) | Long-branched chain polyacrylamide copolymer and preparation method thereof | |
| CN102703042B (en) | Alkali-proof polymer-type profile control agent and preparation method thereof | |
| CN104448712A (en) | Organic fluorine modified epoxy LED packaging material and preparation method thereof | |
| CN102633960A (en) | Multi-environmental-sensitivity triblock copolymer and preparation method and application thereof | |
| CN103059212A (en) | Hydrogenated rosin modified acrylic ester hybridization emulsion and preparation method and application thereof | |
| CN103570858A (en) | Cation polyvinyl acetate emulsion for stabilization of sands and preparation method thereof | |
| CN104693469A (en) | Preparation method of highly ordered flexible colloidal crystal thin film | |
| CN104371691A (en) | Hydrophobically associating polymer sulfonate oil-displacing agent and synthesizing method thereof | |
| CN107417861A (en) | A kind of preparation method of salt tolerance water shutoff agent | |
| CN113185630A (en) | Biodegradable salt-tolerant thickening system and preparation method and application thereof | |
| CN103319640B (en) | A kind of preparation method of styrene-acrylic resin with high solid content | |
| CN103232566B (en) | Preparation method of high-solid-content low-viscosity acrylate emulsion for sealing gum | |
| CN105331054B (en) | A kind of composite conductive thin film | |
| CN102746439A (en) | Preparation method of end group functionalized acrylonitrile homopolymer or copolymer | |
| CN102924640B (en) | Method for preparing branched polystyrene by emulsion polymerization | |
| CN103406067A (en) | Polycarboxylic acid dispersing agent and preparation method and application thereof | |
| CN108130065A (en) | A kind of nano-complex for being used to improve high temperature flooding polymers long-time stability | |
| CN104672368A (en) | Preparation method of form-adjustable anisotropic asymmetric emulsion particles | |
| CN106146731A (en) | Heat-resistant salt-resistant viscoelasticity microsphere and preparation method thereof | |
| CN101735401A (en) | In-situ polymerization technology for preparing anti-settling luminous acrylic resin | |
| CN102453252A (en) | Acrylamide macromonomer and comb type copolymer and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |