CN1583814A - Interpenetrating mono-amine/epoxy emulsion resin cured at atmosphere and its synthesis - Google Patents
Interpenetrating mono-amine/epoxy emulsion resin cured at atmosphere and its synthesis Download PDFInfo
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- CN1583814A CN1583814A CN 200410019484 CN200410019484A CN1583814A CN 1583814 A CN1583814 A CN 1583814A CN 200410019484 CN200410019484 CN 200410019484 CN 200410019484 A CN200410019484 A CN 200410019484A CN 1583814 A CN1583814 A CN 1583814A
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Abstract
An interpenetrating polymer networks monomer amidocyanogen/epoxy type emulsion resin cured at atmosphere is achieved. The inner layer of above copolymer emulsified liquid is primary amine group contained compound, styrene, acrylic acid ester and methylacrylic acid ester copolymers. Middle network layers are acrylic acid easter, methylacrylic acid ester, glycoldimethyl acrylic ester and acrylic acid copolymers. External layers are epoxy group contained methylacrylic acid glycide ester polymer. The process includes synthesis of double bond contained and primary amine contained compound A, and compound A contained copolymer emulsion liquid's preparation, The invention's advantages are improving the emulsion film's mechanical capability, and realizing monomer component in room temperature condition solidifing.
Description
Technical field
The present invention relates to form interpenetrating(polymer)networks single component amido/epoxy type self-vulcanizing emulsion resin and synthetic after a kind of film forming, belong to the emulsion coatings technology.
Background technology
People (Effect of cross-linking on polymer diffusion inpoly (butyl methacrylate-co-butyl acrylate) latex films such as Toshiyuki Tamai, Macromolecules, 1999,32,6102) the research crosslinking structure to butyl methacrylate and butyl acrylate copolymer emulsion film in during the diffusion of polymer chain, discovery does not have solvent resistance by ethylene glycol dimethacrylate as the emulsion polymer films of linking agent, the reason that causes this result is that the swelling of solvent makes suspension chain and terminal chain generation disentanglement between the cross-linking set that had spread the interface in the cross-linked network, be confined to the crosslinked tensile property that can improve film of emulsion particle inside, but can not improve the solvent resistance of film.One can be proposed thus and film properties can be improved, can improve the method for solvent resistance again: contain reactive functional groups in the promptly lightly crosslinked emulsion particle, crosslinking reaction can take place in film forming and segment diffusion back in this functional group, so just can fix and spread good entangled chain, thus the contradiction that solution mechanical strength and solvent resistance are difficult to get both.
Summary of the invention
The object of the present invention is to provide a kind of interpenetrating(polymer)networks single component amido/epoxy type self-vulcanizing emulsion resin and synthetic, this emulsion resin not only has good film-forming properties and film properties, and VOCs content low, have good water tolerance and a solvent resistance, the preparation method is simple, can be widely used in coating and tamanori.
The present invention is achieved by following technical proposals: this interpenetrating(polymer)networks single component amido/epoxy type self-vulcanizing emulsion resin, it is characterized in that, the multipolymer internal layer is to contain the compound of primary amine group and methacrylic ester, acrylate, cinnamic multipolymer, the go-between layer is the multipolymer of acrylate, ethylene glycol dimethacrylate and methacrylic ester, and is outer for containing the glycidyl methacrylate polymkeric substance of epoxy-functional.
The synthetic method of above-mentioned emulsion resin is characterized in that comprising following process:
1. compd A synthetic that has unsaturated double-bond and primary amine group: the acid anhydrides and the quadrol that maleic anhydride, FUMARIC ACID TECH GRADE acid anhydride or itaconic anhydride are contained unsaturated double-bond are dissolved in the tetrahydrofuran (THF) respectively, according to the molar ratio of acid anhydrides and quadrol be 1.0～1.5 proportioning 20～35 ℃ of reactions, product obtains being with the primary amine group compd A through washing, filtration, drying.
2. contain the preparation of the copolymer emulsion of compd A:
A) preparation of internal layer copolymer emulsion: at first with compd A, methacrylic ester, ethyl propenoate and vinylbenzene are by 1: (11～22): (12～22): (0.5～2) mass ratio mixes, add the emulsifying agent MS-1 that accounts for total monomer amount 2.0～3.0wt%, said mixture is joined in the deionized water, be made into the mixed solution that monomer content is 20.0～40.0wt%, logical nitrogen protection, and in 65～80 ℃ of following 15～50min that stir, add ammonium persulphate class initiator again and make seed emulsion, and slowly, evenly dripping by methacrylic ester and ethyl propenoate is 1 by mass ratio: the solution that (1～2) is made into, drip simultaneously and contain ammonium persulphate, the aqueous solution of sodium bicarbonate, after dropwising, under this temperature, be incubated 2.0～4.0h;
B) preparation of network layer copolymer emulsion: at the internal layer copolymer emulsion that a) prepares, the MS-1 aqueous solution that adds total monomer amount 0.6～1.0wt%, slow behind the 30min, the even dropping by ethyl propenoate, ethylene glycol dimethacrylate, methyl methacrylate and vinylformic acid is 1 in mass ratio: (0.002～0.05): (0.2～0.5): the solution that the ratio of (0.01～0.05) is made into, the dropping time is 4.0～5.0h, after waiting to dropwise, insulation 3.0～4.0h;
C) preparation of outer layer copolymer emulsion: with b) the network copolymer emulsion that makes is cooled to 40～50 ℃, adding concentration behind the 30min is the 10wt% sodium sulfite solution, wherein the amount of sodium bisulfite is the 1.0wt% of total monomer quality, the aqueous solution that the Sodium Persulfate of slow behind the 5min, even dropping and sodium bisulfite equivalent is made into, dropping accounts for the glycidyl methacrylate of 3.0～6.0wt% of total monomer amount, the dropping time is 1.0～3.0h, dropwises the back and be incubated 2.0～3.0h under this temperature; Regulate pH value to 6.0～7.0 with sodium hydroxide solution at last, obtain copolymer emulsion.
The invention has the advantages that: the compound of selecting two keys of the acid anhydrides that contains unsaturated double-bond and binary primary amine prepared in reaction band and primary amine group for use.Make this synthetics carry out emulsion copolymerization with other monomer; Has simultaneously the reactive behavior of primary amine again.Because this synthetics molecular weight is big, non-volatile, reduced micromolecular binary primary amine because the infringement that volatilization causes people or environment.Owing to implement emulsion copolymerization, the volatile organic content in reduction or the elimination coating.While utilization of the present invention office is in the change technology, earlier primary amine is fixed in the internal layer of latex granule, synthetic then certain thickness middle layer, and, at last the compound of band oxygen groups is positioned the skin of emulsion particle at middle layer spent glycol dimethacrylate formation network.Make between the network cross-linked point suspension chain after crosslinked, potential reactive functionality primary amine group and epoxide group generation crosslinking reaction, form interpenetrating(polymer)networks with crosslinking structure original in the emulsion particle, fixed the suspension chain after the diffusion, solvent resistance, water tolerance and the mechanical property of polymeric film are greatly improved.And the present invention has realized that also single component solidifies at ambient temperature.
Embodiment
Example 1
The 20g maleic anhydride is dissolved in the 60g tetrahydrofuran (THF), the 13.0g quadrol is dissolved in the 90g tetrahydrofuran (THF).Maleic anhydride solution slowly is added drop-wise to (rate of addition is 1ml/min) in the ethylenediamine solution, 20 ~ 22 ℃ of reactions down.The product that obtains is washed four times with tetrahydrofuran (THF), and behind filtration under diminished pressure, drying under reduced pressure makes about 24.75g maleic anhydride list quadrol acid amides.
1.61g maleic anhydride list quadrol acid amides, 2.30g vinylbenzene, 32.20g methyl methacrylate, 34.50g ethyl propenoate, 2.40g emulsifying agent MS-1,161.0g deionized water are joined in the reactor that has thermometer, condenser, agitator and nitrogen protection device, and stir 40min under 75 ℃ of temperature.Add and contain 0.414g ammonium persulphate and 0.046g sodium bicarbonate aqueous solution, wherein, the concentration of ammonium persulphate is 4.30wt%, initiated polymerization.Behind the question response 30min, keep 75 ℃ of temperature of reaction, slowly drip the solution that is made into by 20.7g methyl methacrylate, 25.30g ethyl propenoate, rate of addition is 0.90ml/min, slowly drip simultaneously and contain 0.414g ammonium persulphate, 0.046g sodium bicarbonate aqueous solution, wherein, ammonium persulphate concentration is 4.30wt%, and rate of addition is 0.14ml/min.After waiting to dropwise, under this temperature, be incubated 2.5h.Add 24.84g MS-1 emulsifier aqueous solution, wherein the content of MS-1 is 1.84g.After stirring 30min, drip the solution that is made into by 78.2g ethyl propenoate, 26.45g methyl methacrylate, 1.16g vinylformic acid and 0.23g ethylene glycol dimethacrylate lentamente, rate of addition is: 0.2ml/min, contain 0.952g ammonium persulphate, 0.106g sodium bicarbonate aqueous solution lentamente simultaneously, wherein ammonium persulphate concentration is 4.30wt%, and rate of addition is 0.14ml/min.After waiting to dropwise, under this temperature, be incubated 2.0h.
Above-mentioned emulsion is cooled to 45 ℃, add the 13.80g sodium sulfite solution behind the 30min, wherein the content of sodium bisulfite is 2.3g, slowly, evenly drip behind the 5min and contain 4.6g Sodium Persulfate and 0.046g sodium bicarbonate aqueous solution, wherein ammonium persulphate concentration is 3.85wt%, rate of addition is 0.35ml/min, drip the 6.90g glycidyl methacrylate simultaneously, the dropping time is 1.0h, dropwise the back and under this temperature, be incubated 2.0h, regulate pH value to 6.0～7.0 with sodium hydroxide solution, obtain copolymer emulsion.
With above-mentioned emulsion drying and forming-film under 30 ℃ of conditions, make 60mm * 20mm, thickness is about the sample of 1.0mm, behind the dry 24h, at 90 ℃ of slaking 90min, with the sample test tensile strength on M350-10KN type electronic tensile machine that makes.Draw speed is 100mm/min, and tensile strength is 7.423MPa.The polymeric film that makes is made water resistance test, and the 72h water-intake rate is 17.69%.This film soaks 24h in tetrahydrofuran (THF), do not occur damaged.
Example 2
Adopt the method identical to prepare maleic anhydride list oxalamide with example 1.1.84g maleic anhydride list quadrol acid amides, 2.30g vinylbenzene, 32.20g methyl methacrylate, 34.50g ethyl propenoate, 2.40g emulsifying agent MS-1,161.0g deionized water are joined in the reactor that has thermometer, condenser, agitator and nitrogen protection device, and stir 40min under 75 ℃ of temperature.Add and contain 0.414g ammonium persulphate, 0.046g sodium bicarbonate aqueous solution, wherein ammonium persulphate concentration is 4.30wt%, initiated polymerization.Behind the question response 30min, keep 75 ℃ of temperature of reaction, slowly drip the solution that is made into by 20.7g methyl methacrylate, 25.30g ethyl propenoate, rate of addition is 0.90ml/min, slowly drip simultaneously and contain 0.414g ammonium persulphate, 0.046g sodium bicarbonate aqueous solution, wherein ammonium persulphate concentration is 4.30wt%, and rate of addition is 0.14ml/min.After waiting to dropwise, under this temperature, be incubated 2.5h.Add 24.84g MS-1 emulsifier aqueous solution, wherein the content of MS-1 is 1.84g.After stirring 30min, drip the solution that is made into by 78.2g ethyl propenoate, 26.45g methyl methacrylate, 1.16g vinylformic acid and 0.23g ethylene glycol dimethacrylate lentamente, rate of addition is: 0.2ml/min, drip simultaneously and contain 0.952g ammonium persulphate, 0.106g sodium bicarbonate aqueous solution, wherein ammonium persulphate concentration is 4.30wt%, and rate of addition is 0.14ml/min.After waiting to dropwise, under this temperature, be incubated 2.0h.
Above-mentioned emulsion is cooled to 45 ℃, add the 13.80g sodium sulfite solution behind the 30min, wherein the content of sodium bisulfite is 2.3g, slowly, evenly drip behind the 5min and contain 4.6g Sodium Persulfate and 0.046g sodium bicarbonate aqueous solution, wherein ammonium persulphate concentration is 3.85%wt, rate of addition is 0.35ml/min, drip the 6.90g glycidyl methacrylate simultaneously, the dropping time is 1.0h, dropwise the back and under this temperature, be incubated 2.0h, regulate pH value to 6.0～7.0 with sodium hydroxide solution, obtain copolymer emulsion.
With above-mentioned emulsion drying and forming-film under 30 ℃ of conditions, make 60mm * 20mm, thickness is about the sample of 1.0mm, behind the dry 24h, at 90 ℃ of slaking 90min, with the sample that makes in M350-10KN type electronic tensile machine test tensile strength.Draw speed is 100mm/min, and tensile strength is 8.226MPa.To make polymeric film and make water resistance test, the 72h water-intake rate is 16.73%.This film soaks 24h in tetrahydrofuran (THF), do not occur damaged.
Example 3
Adopt the method identical to prepare maleic anhydride list oxalamide with example 1.2.76g maleic anhydride list quadrol acid amides, 2.30g vinylbenzene, 32.20g methyl methacrylate, 34.50g ethyl propenoate, 2.40g emulsifying agent MS-1,161.0g deionized water are joined in the reactor that has thermometer, condenser, agitator and nitrogen protection device, and stir 40min under 75 ℃ of temperature.Add and contain 0.414g ammonium persulphate, 0.046g sodium bicarbonate aqueous solution, wherein ammonium persulphate concentration is 4.30wt%, initiated polymerization.Behind the question response 30min, keep 75 ℃ of temperature of reaction, slowly drip the solution that is made into by 20.7g methyl methacrylate, 25.30g ethyl propenoate, rate of addition is 0.90ml/min, slowly drip simultaneously and contain 0.414g ammonium persulphate, 0.046g sodium bicarbonate aqueous solution, wherein ammonium persulphate concentration is 4.30wt%, and rate of addition is 0.14ml/min.After waiting to dropwise, under this temperature, be incubated 2.5h.Add 24.84g MS-1 emulsifier aqueous solution, wherein the amount of MS-1 is 1.84g.After stirring 30min, drip the solution that is made into by 78.2g ethyl propenoate, 26.45g methyl methacrylate, 1.16g vinylformic acid and 0.23g ethylene glycol dimethacrylate lentamente, rate of addition is 0.2ml/min, drip simultaneously and contain 0.952g ammonium persulphate, 0.106g sodium bicarbonate aqueous solution, wherein ammonium persulphate concentration is 4.30wt%, and rate of addition is 0.14ml/min.After waiting to dropwise, under this temperature, be incubated 2.0h.
Above-mentioned emulsion is cooled to 45 ℃, add the 13.80g sodium sulfite solution behind the 30min, wherein the content of sodium bisulfite is 2.3g, slowly, evenly drip behind the 5min and contain 4.6g Sodium Persulfate and 0.046g sodium bicarbonate aqueous solution, wherein ammonium persulphate concentration is 3.85wt%, rate of addition is 0.35ml/min, drip the 6.90g glycidyl methacrylate simultaneously, the dropping time is 1.0h, dropwise the back and under this temperature, be incubated 2.0h, regulate pH value to 6.0～7.0 with sodium hydroxide solution, obtain copolymer emulsion.
With above-mentioned emulsion drying and forming-film under 30 ℃ of conditions, make 60mm * 20mm, thickness is about the sample of 1.0mm, behind the dry 24h, behind 90 ℃ of slaking 90min, with the sample that makes in M350-10KN type electronic tensile machine test tensile strength.Draw speed is 100mm/min, and tensile strength is 6.769MPa.Make water resistance test with the polymeric film that makes, the 72h water-intake rate is 12.33%.This film soaks 24h in tetrahydrofuran (THF), disrepair phenomenon do not occur.
Claims (2)
1. interpenetrating(polymer)networks single component amido/epoxy type self-vulcanizing emulsion resin, it is characterized in that: the internal layer of this multipolymer is to contain the compound of primary amine group and methacrylic ester, acrylate, cinnamic multipolymer, the go-between layer is the multipolymer of acrylate, ethylene glycol dimethacrylate and methacrylic ester, and is outer for containing the glycidyl methacrylate polymkeric substance of epoxy-functional.
2. the preparation method by the described interpenetrating(polymer)networks single component amido of claim 1/epoxy type self-vulcanizing emulsion resin is characterized in that comprising the following steps:
1) have compd A synthetic of unsaturated double-bond and primary amine group: the acid anhydrides and the quadrol that maleic anhydride, FUMARIC ACID TECH GRADE acid anhydride or itaconic anhydride are contained unsaturated double-bond are dissolved in the tetrahydrofuran (THF) respectively, according to the molar ratio of acid anhydrides and quadrol be 1.0～1.5 proportioning 20～35 ℃ of reactions, product obtains being with the primary amine group compd A through washing, filtration, drying;
2) contain the preparation of the copolymer emulsion of compd A:
A) preparation of internal layer copolymer emulsion: at first with compd A, methacrylic ester, ethyl propenoate and vinylbenzene are by 1: (11～22): (12～22): (0.5～2) mass ratio mixes, add the emulsifying agent MS-1 that accounts for total monomer amount 2.0～3.0wt%, said mixture is joined in the deionized water, be made into the mixed solution that monomer content is 20.0～40.0wt%, logical nitrogen protection, and in 65～80 ℃ of following 15～50min that stir, add ammonium persulphate class initiator again and make seed emulsion, and slowly, evenly dripping by methacrylic ester and ethyl propenoate is 1 by mass ratio: the solution that (1～2) is made into, drip simultaneously and contain ammonium persulphate, the aqueous solution of sodium bicarbonate, after dropwising, under this temperature, be incubated 2.0～4.0h;
B) preparation of network layer copolymer emulsion: at the internal layer copolymer emulsion that a) prepares, the MS-1 aqueous solution that adds total monomer amount 0.6～1.0wt%, slow behind the 30min, the even dropping by ethyl propenoate, ethylene glycol dimethacrylate, methyl methacrylate and vinylformic acid is 1 in mass ratio: (0.002～0.05): (0.2～0.5): the solution that the ratio of (0.01～0.05) is made into, the dropping time is 4.0～5.0h, after waiting to dropwise, insulation 3.0～4.0h;
C) preparation of outer layer copolymer emulsion: with b) the network copolymer emulsion that makes is cooled to 40～50 ℃, adding concentration behind the 30min is the 10wt% sodium sulfite solution, wherein the amount of sodium bisulfite is the 1.0wt% of total monomer quality, slowly, evenly drip the aqueous solution that is made into the normal Sodium Persulfate of sodium bisulfite behind the 5min, dropping accounts for the glycidyl methacrylate of 3.0～6.0wt% of total monomer amount, the dropping time is 1.0～3.0h, dropwises the back and be incubated 2.0～3.0h under this temperature; Regulate pH value to 6.0～7.0 with sodium hydroxide solution at last, obtain copolymer emulsion.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111303333A (en) * | 2018-12-11 | 2020-06-19 | 万华化学集团股份有限公司 | Quick-drying water-based acrylic polymer emulsion and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111303333A (en) * | 2018-12-11 | 2020-06-19 | 万华化学集团股份有限公司 | Quick-drying water-based acrylic polymer emulsion and preparation method and application thereof |
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