CN103626936A - Water-resistant and high temperature-resistant polymer latex and preparation method thereof - Google Patents
Water-resistant and high temperature-resistant polymer latex and preparation method thereof Download PDFInfo
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- CN103626936A CN103626936A CN201310699831.8A CN201310699831A CN103626936A CN 103626936 A CN103626936 A CN 103626936A CN 201310699831 A CN201310699831 A CN 201310699831A CN 103626936 A CN103626936 A CN 103626936A
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Abstract
The invention relates to water-resistant and high temperature-resistant polymer latex and a preparation method thereof. The latex provided by the invention mainly comprises the following polymerization monomers in percentage by weight: 0-80wt% of C5-C11 acrylic ester, 10-75wt% of C4-C5 aliphatic conjugated dienes, 15-80wt% of C8-C9 aromatic vinyl compounds, 0-10wt% of acrylonitrile, 1-5wt% of C3-C5 vinyl unsaturated carboxylic acid and 0.3-2.5wt% of C3-C4 unsaturated amide. The latex provided by the invention has proper particle size, viscosity and stability, and latex impregnated paper produced from the latex has excellent water resistance and high temperature resistance.
Description
Technical field
The invention belongs to chemical field, relate in particular to a kind of latex and preparation method thereof.
Background technology
Polymer latex is widely used in the industries such as papermaking, carpet and building, in application process, more and more higher to the performance requriements of latex.In the production process of latex dipping paper, except requiring latex to have good technique suitability, the water tolerance of latex polymer and temperature tolerance have been proposed to particular requirement.
Previous patent is if JP61-63795, CN1208737 and CN1427018 are when the synthetic latex, by use more water-soluble unsaturated monomer as: functional monomer and the anionic and nonionic composite emulsifying systems such as vinylformic acid, acrylamide and N hydroxymethyl acrylamide, obtained the good carboxylate latex of stability.The latex of preparing by these methods, can meet the requirement to latex such as White Board and carpet backing, yet by these latex during for the production of latex dipping paper, water tolerance and the resistance to elevated temperatures of finished paper do not reach requirement.
Summary of the invention
technical problem
In view of this, the technical problem to be solved in the present invention is to have the latex of good water tolerance and high thermal resistance.
solution
In order to solve the problems of the technologies described above, the invention provides a kind of water resistant, high temperature resistant polymer latex, it is characterized in that, mainly comprise that following weight is than polymerization single polymerization monomer:
Acrylate 0～80wt% of C5～C11, aliphatics Conjugated Diolefin hydrocarbon 10～75wt% of C4～C5, aromatic ethenyl compound 15～80wt% of C8～C9, vinyl cyanide 0～10wt%, vinyl unsaturated carboxylic acid 1～5wt% of C3～C5, unsaturated amides 0.3～2.5wt% of C3～C4.
Preferably, described acrylate is one or more compounds in methyl methacrylate vinegar, butyl acrylate, Octyl acrylate;
Described aliphatics Conjugated Diolefin hydrocarbon is one or more compounds in divinyl, isoprene;
Described aromatic ethenyl compound is one or more compounds in vinylbenzene, a-vinyl toluene;
Described vinyl unsaturated carboxylic acid is one or more compounds in vinylformic acid, methylene-succinic acid;
Described unsaturated amides is one or more compounds of acrylamide, n-methylolacrylamide.
Preferably, a kind of preparation method of water resistant, high temperature resistant polymer latex, is characterized in that,
By polymerization single polymerization monomer and anionic emulsifier, reactive emulsifier, reactive antioxidant, carrying out polyreaction at 70～100 ℃ makes;
The add-on of described anionic emulsifier, reactive emulsifier is 0.2～8wt% of reaction monomers weight;
The add-on of described reactive antioxidant is 0.2～1.5wt% of reaction monomers weight.
Preferably, a kind of preparation method of water resistant, high temperature resistant polymer latex, one or more compounds in the alkyl aryl ether sodium sulfonate of the sodium alkyl sulfate that described anionic emulsifier is C10～C18, the sodium alkyl benzene sulfonate of C10～C18, C10～C18;
Described reactive emulsifier is one or more compounds in allyloxy fatty alcohol oxygen Vinyl Ether ammonium sulfate, acrylamido sodium isopropyl xanthate;
Described reactive antioxidant is one or more compounds in anilino phenyl methyl acrylamide, 2,2 '-Ding fork two (6-tert-butyl-4-methyl-Phenol).
When latex of the present invention is synthetic, initiator is thermal initiator if persulfuric acid is by, Potassium Persulphate, polymerization temperature is between 75～95 ℃, the mode that adds of unsaturated acid acid, unsaturated amides can be disposable adding also to add in batches, emulsifying agent equally also can disposablely add or add in batches, the mode that adds of monomer be disposable, add or add continuously in batches.
beneficial effect
Latex provided by the invention is the multiple copolymer latex that contains unsaturated carboxylic acid, unsaturated amides and vinyl monomer, has adopted reactive emulsifier and reactive antioxidant during polymerization.The polymer latex that adopts method of the present invention to make has suitable viscosity, particle diameter and stability, with the impregnated paper that this latex is produced, has good water tolerance and high thermal resistance.
Latex provided by the invention is the many monomer copolymers that contain acrylate, aliphatics Conjugated Diolefin hydrocarbon, aromatic ethenyl compound, vinyl cyanide, unsaturated carboxylic acid and unsaturated amides.Latex has adopted reactive emulsifier, reactive antioxidant when synthetic.This latex adopts appropriate emulsifying agent and functional monomer to make, and has suitable particle diameter, viscosity and stability, with the latex dipping paper that this latex is produced, has good water tolerance and high thermal resistance.
Embodiment
Embodiment 1 (take total monomer add-on as 100wt%):
In 50L polymeric kettle, first vacuumize, use again nitrogen replacement, during reach-0.08MPa of vacuum tightness, adding the water yield is 70wt%, sodium lauryl sulphate 0.4wt%, allyloxy fatty alcohol oxygen Vinyl Ether ammonium sulfate 0.35wt%, Repone K 0.06wt%, sodium hydroxide 0.86wt%, methyl methacrylate 3wt%, vinylbenzene 12wt%, tert-dodecyl mercaptan 0.3wt%, vinylformic acid 2wt%, methylene-succinic acid 1wt%, acrylamide 1wt%, divinyl 10wt%, then start to stir and be warmed up to 70 degree, add initiator ammonium persulfate 1.5wt% to maintain polyreaction after 1 hour, by water 30wt%, sodium lauryl sulphate 0.3wt%, tert-dodecyl mercaptan 0.2wt%, vinylbenzene 34wt%, anilino phenyl methyl acrylamide 0.5wt%, divinyl 25wt%, after the mixture of methyl methacrylate 12wt% added continuously in 4 hours, slaking is 3 hours, polymerisation conversion reaches more than 98%, add the auxiliary agents such as appropriate potassium hydroxide and defoamer, remove residual monomer, latex technology index is in Table 2, latex dipping paper technical indicator is in Table 3.
Embodiment 2 (take total monomer add-on as 100wt%)
In 50L polymeric kettle, first vacuumize, use again nitrogen replacement, during reach-0.08MPa of vacuum tightness, add water 100wt%, dodecyl aryl ethers sodium sulfonate 1.0wt%, Sodium dodecylbenzene sulfonate 0.2wt%, , acrylamido sodium isopropyl xanthate 0.4wt%, Repone K 0.05wt%, sodium hydroxide 0.2wt%, butyl acrylate 8wt%, 2, two (6-tert-butyl-4-methyl-Phenol) 0.6wt% of 2 '-Ding fork, vinylbenzene 36wt%, tert-dodecyl mercaptan 0.5wt%, vinylformic acid 3wt%, methyl methacrylate 20wt%, n-methylolacrylamide 1wt%, divinyl, 32wt%, then start to stir and be warmed up to 65 degree, add initiator ammonium persulfate 1.0wt% polyreaction 8 hours, transformation efficiency reaches more than 98%, add the auxiliary agents such as appropriate potassium hydroxide and defoamer, remove residual monomer, latex technology index is in Table 2, latex dipping paper technical indicator is in Table 3.
Embodiment 3 (take total monomer add-on as 100wt%)
In 50L polymeric kettle, first vacuumize, use again nitrogen replacement, during reach-0.08MPa of vacuum tightness, adding the water yield is 80wt%, sodium stearyl sulfate 0.2wt%, allyloxy fatty alcohol oxygen Vinyl Ether ammonium sulfate 0.3wt%, Repone K 0.06wt%, sodium hydroxide 0.83wt%, a-vinyl toluene 15wt%, tert-dodecyl mercaptan 0.3wt%, vinylformic acid 1.8wt%, acrylonitrile 8wt%, acrylamide 1.2wt%, divinyl 12wt%, then start to stir and be warmed up to 70 degree, add initiator ammonium persulfate 1wt%, maintain polyreaction and after 1 hour, add continuously water 20wt%, sodium lauryl sulphate 0.5wt%, tert-dodecyl mercaptan 0.2wt%, ammonium persulphate 0.2wt%, 2, two (6-tert-butyl-4-methyl-Phenol) 0.6wt% of 2 '-Ding fork, vinylbenzene 32wt%, the mixture of divinyl 30wt% continues polymerization 4 hours, polymerisation conversion reaches more than 98%, add the auxiliary agents such as appropriate potassium hydroxide and defoamer, remove residual monomer, latex technology index is in Table 2, latex dipping paper technical indicator is in Table 3.
Embodiment 4,5.6, and 7 adopt the polymerization process of embodiment 1 to implement respectively, and the add-on of monomer and auxiliary agent is in Table 1, and latex technology index is in Table 2, and latex dipping paper technical indicator is in Table 3.
Comparative example 1,2,3,4 adopt the polymerization process of embodiment 1 to carry out respectively, and the add-on of monomer and auxiliary agent is in Table 1, and latex technology index is in Table 2, and latex dipping paper technical indicator is in Table 3.
The add-on of table 1 embodiment 1-7 and comparative example 1-4 emulsifying agent, anti-aging agent and monomer
The technical indicator contrast of table 2 embodiment 1-7 and comparative example 1-4 gained latex
Use SH/T1154-92 method to measure solid content; Use SH/T1152-92 method to measure viscosity of latex, SH/T1151-92 method is measured mechanical stability, and SH/T1150-92 method is measured pH value, uses the AUTOSIZER I I C type particle instrument of Britain to survey the equal particle diameter of Z.
Impregnated paper performance prepared by table 3 embodiment 1-7 and comparative example 1-4 gained latex
Water tolerance: refer to that latex dipping paper occurs to paper the time that breakthrough is required from starting to contact water, general requirement is greater than 6 minutes;
Tension stress, elongation: the DLS-3 type electronic paper tensile strength meter and the determination of test method that adopt Jinan Ming Wei detection technique company limited to produce;
150 ℃ are aging: refer to first latex dipping paper placed 2 hours in 150 ℃ of constant temperature ovens, and room temperature after standing 1 hour then, then test latex dipping paper performance;
180 ℃ aging again: refer to first latex dipping paper placed 2 hours in 150 ℃ of constant temperature ovens, room temperature is after standing 1 hour; Put into 180 ℃ of constant temperature ovens 2 hours, room temperature is after standing 1 hour again, then tests latex dipping paper performance.
Latex provided by the invention has suitable particle diameter, viscosity and stability, with the latex dipping paper that this latex is produced, has good water tolerance and high thermal resistance.
The above; be only the specific embodiment of the present invention, but protection scope of the present invention is not limited to this, is anyly familiar with those skilled in the art in the technical scope that the present invention discloses; can expect easily changing or replacing, within all should being encompassed in protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion by the described protection domain with claim.
Claims (4)
1. a water resistant, high temperature resistant polymer latex, is characterized in that, mainly comprises that following weight is than polymerization single polymerization monomer:
Acrylate 0～80wt% of C5～C11, aliphatics Conjugated Diolefin hydrocarbon 10～75wt% of C4～C5, aromatic ethenyl compound 15～80wt% of C8～C9, vinyl cyanide 0～10wt%, vinyl unsaturated carboxylic acid 1～5wt% of C3～C5, unsaturated amides 0.3～2.5wt% of C3～C4.
2. water resistant, high temperature resistant polymer latex according to claim 1, is characterized in that,
Described acrylate is one or more compounds in methyl methacrylate vinegar, butyl acrylate, Octyl acrylate;
Described aliphatics Conjugated Diolefin hydrocarbon is one or more compounds in divinyl, isoprene;
Described aromatic ethenyl compound is one or more compounds in vinylbenzene, a-vinyl toluene;
Described vinyl unsaturated carboxylic acid is one or more compounds in vinylformic acid, methylene-succinic acid;
Described unsaturated amides is one or more compounds of acrylamide, n-methylolacrylamide.
3. a preparation method for water resistant, high temperature resistant polymer latex as claimed in claim 1 or 2, is characterized in that,
By polymerization single polymerization monomer and anionic emulsifier, reactive emulsifier, reactive antioxidant, carrying out polyreaction at 70～100 ℃ makes;
The add-on of described anionic emulsifier, reactive emulsifier is 0.2～8wt% of reaction monomers weight;
The add-on of described reactive antioxidant is 0.2～1.5wt% of reaction monomers weight.
4. the preparation method of water resistant, high temperature resistant polymer latex according to claim 3, is characterized in that,
Described anionic emulsifier is that the sodium alkyl sulfate of C10～C18 is, one or more compounds in the alkyl aryl ether sodium sulfonate of the sodium alkyl benzene sulfonate of C10～C18, C10～C18;
Described reactive emulsifier is one or more compounds in allyloxy fatty alcohol oxygen Vinyl Ether ammonium sulfate, acrylamido sodium isopropyl xanthate;
Described reactive antioxidant is one or more compounds in anilino phenyl methyl acrylamide, 2,2 '-Ding fork two (6-tert-butyl-4-methyl-Phenol).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104761671A (en) * | 2015-03-31 | 2015-07-08 | 东华大学 | Preparation method of polyacrylonitrile nano latex particles |
| CN104788600A (en) * | 2014-12-26 | 2015-07-22 | 上海强盛化工有限公司 | Emulsion and preparation method thereof |
| CN109081886A (en) * | 2018-08-21 | 2018-12-25 | 济宁明升新材料有限公司 | A kind of preparation method and application of styrene-butadiene latex |
| CN111138581A (en) * | 2020-01-17 | 2020-05-12 | 日照广大建筑材料有限公司 | Isoprene latex and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1427018A (en) * | 2001-12-17 | 2003-07-02 | 中国石油天然气集团公司 | High stability corboxylic latex |
| CN102653579A (en) * | 2011-03-03 | 2012-09-05 | 中国石油天然气股份有限公司 | Nitrile rubber and preparation method thereof |
-
2013
- 2013-12-18 CN CN201310699831.8A patent/CN103626936A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1427018A (en) * | 2001-12-17 | 2003-07-02 | 中国石油天然气集团公司 | High stability corboxylic latex |
| CN102653579A (en) * | 2011-03-03 | 2012-09-05 | 中国石油天然气股份有限公司 | Nitrile rubber and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104788600A (en) * | 2014-12-26 | 2015-07-22 | 上海强盛化工有限公司 | Emulsion and preparation method thereof |
| CN104761671A (en) * | 2015-03-31 | 2015-07-08 | 东华大学 | Preparation method of polyacrylonitrile nano latex particles |
| CN109081886A (en) * | 2018-08-21 | 2018-12-25 | 济宁明升新材料有限公司 | A kind of preparation method and application of styrene-butadiene latex |
| CN111138581A (en) * | 2020-01-17 | 2020-05-12 | 日照广大建筑材料有限公司 | Isoprene latex and preparation method thereof |
| CN111138581B (en) * | 2020-01-17 | 2022-05-06 | 日照广大建筑材料有限公司 | Isoprene latex and preparation method thereof |
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Application publication date: 20140312 |