CN1298760C - Method for preparing compound emulsion of dimmer of cation polyurethane and alkyl ketene - Google Patents
Method for preparing compound emulsion of dimmer of cation polyurethane and alkyl ketene Download PDFInfo
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- CN1298760C CN1298760C CNB2005100430180A CN200510043018A CN1298760C CN 1298760 C CN1298760 C CN 1298760C CN B2005100430180 A CNB2005100430180 A CN B2005100430180A CN 200510043018 A CN200510043018 A CN 200510043018A CN 1298760 C CN1298760 C CN 1298760C
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Abstract
The present invention relates to a method for preparing cation polyurethane / alkyl group enone dipolymer composite emulsion. Firstly, alkyl group enone dipolymer is added in a drying reactor, the alkyl group enone dipolymer in the reactor is heated and is melted, and then diisocyanate, carbowax and dibutyltin dilaurate are added in the reactor for polycondensation reaction; thereby, an alkyl group enone dipolymer solution is formed; N-methyldiethanolamine is added into the alkyl group enone dipolymer solution for chain propagation reaction, dimethyl sulphate is also added in for quaterisation, and finally, glacial acetic acid is added; after a pH value is adjusted from 4.5 to 6.5, deionized water is added, and then white emulsion of which the solid content is 25% is obtained. The present invention uses the melted alkyl group enone dipolymer as organic solvent for cation polyurethane synthesis reaction, organic solvent required in the preparation process of polyurethane is eliminated, and emulsifier is unnecessarily added in the preparation. Thereby, the present invention eliminates the pollution and the damage of environment and operators, and also improves the application effect of a product.
Description
Technical field
The invention belongs to fine chemicals preparation technology field, particularly a kind of preparation method of compound emulsion of dimmer of cation polyurethane and alkyl ketene.
Background technology
Be widely used owing to polyaminoester emulsion has good physical and chemical performance, but in its preparation process, need to use a large amount of organic solvents and emulsifying agent, staff, environment and effect are had a negative impact.Alkyl ketene dimer has long fat hydrocarbon chain (C
14～16) and quaternary lactonic ring, be lyophobic dust, be commonly used for the paper sizing agent after it is emulsified, but contain a large amount of emulsifying agents equally in the alkyl ketene dimer emulsion, all unfavorable to handling papermaking wastewater and effect, especially to the sizing efficiency of paper.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, provide a kind of and can improve the product application effect, simultaneously the preparation method of the compound emulsion of dimmer of cation polyurethane and alkyl ketene that can not pollute and damage environment and operator.
For achieving the above object, the technical solution used in the present invention is: at first by mass ratio 6.83～10.65% alkyl ketene dimers are joined in the dry reactor, and reactor is heated to 75～90 ℃, after making the alkyl ketene dimer fusion in the reactor, and then by mass ratio the dibutyl tin laurate of 25.63%～30% tolylene diisocyanate, 40～51.26% polyglycol and 0.40～0.47% is joined in the reactor and to carry out polycondensation 1.0～2.5 hours at 75～90 ℃, form the alkyl ketene dimer solution of base polyurethane prepolymer for use as; With mass ratio is that 12.82～15.77% N methyldiethanol amine joins and carries out chain extending reaction in the alkyl ketene dimer solution, and temperature of reaction is 55～70 ℃, and the reaction times is 0.5～1.5 hour; Be that 3.0～5.0% methyl-sulfates join and carry out quaterisation in the reactor again with mass ratio, temperature of reaction is between 65～80 ℃, and the time is 1.0～2.0 hours; Add glacial acetic acid at last and regulate after pH value is 4.5～6.5, stir that to add temperature down be 20-90 ℃ deionized water, get solids content and be 25% white emulsion.
Polyglycol of the present invention is polyether Glycols or polyester diol, and polyether Glycols and polyester diol number average relative molecular mass are respectively 1000 or 2000.
The present invention carries out the fused alkyl ketene dimer building-up reactions of cation polyurethane as organic solvent, not only eliminated the organic solvent that needs in the polyurethane preparation process, and do not need to add emulsifying agent in the whole preparation process, so both eliminated pollution and infringement, also improved the effect of product environment and operator; Simultaneously, the product that can obtain expecting by the kind of regulating polyglycol.
Embodiment
Embodiment 1, at first 6.83% alkyl ketene dimer is joined in the dry reactor by mass ratio, and reactor is heated to 90 ℃, after making the alkyl ketene dimer fusion in the reactor, adding 30% tolylene diisocyanate, 44.88% relative molecular mass by mass ratio again is that the dibutyl tin laurate of 1000 polyether Glycols and 0.47% joins in the reactor and carried out polycondensation 1.0 hours at 90 ℃, forms the alkyl ketene dimer solution of base polyurethane prepolymer for use as; With mass ratio is that 12.82% N methyldiethanol amine joins and carries out chain extending reaction in the alkyl ketene dimer solution, and temperature of reaction is 55 ℃, and the reaction times is 0.5 hour; Be that 5% methyl-sulfate joins and carries out quaterisation in the reactor again with mass ratio, temperature of reaction is 65 ℃, and the time is 1.0 hours; Add glacial acetic acid at last and regulate after pH value is 4.5, stir that to add temperature down be 20 ℃ deionized water, get solids content and be 25% white emulsion.
Embodiment 2, at first 10.65% alkyl ketene dimer is joined in the dry reactor by mass ratio, and reactor is heated to 75 ℃, after making the alkyl ketene dimer fusion in the reactor, adding 25.63% tolylene diisocyanate, 44.55% relative molecular mass by mass ratio again is that the dibutyl tin laurate of 2000 polyether Glycols and 0.40% joins in the reactor and carried out polycondensation 1.8 hours at 75 ℃, forms the alkyl ketene dimer solution of base polyurethane prepolymer for use as; With mass ratio is that 15.77% N methyldiethanol amine joins and carries out chain extending reaction in the alkyl ketene dimer solution, and temperature of reaction is 60 ℃, and the reaction times is 1.5 hours; Be that 3% methyl-sulfate joins and carries out quaterisation in the reactor again with mass ratio, temperature of reaction is 80 ℃, and the time is 1.2 hours; Add glacial acetic acid at last and regulate after pH value is 6.0, stir that to add temperature down be 90 ℃ deionized water, get solids content and be 25% white emulsion.
Embodiment 3, at first 10% alkyl ketene dimer is joined in the dry reactor by mass ratio, and reactor is heated to 80 ℃, after making the alkyl ketene dimer fusion in the reactor, adding 30% tolylene diisocyanate, 40% relative molecular mass by mass ratio again is that the dibutyl tin laurate of 1000 polyester binary pure and mild 0.45% joins in the reactor and carried out polycondensation 2.3 hours at 80 ℃, forms the alkyl ketene dimer solution of base polyurethane prepolymer for use as; With mass ratio is that 15.55% N methyldiethanol amine joins and carries out chain extending reaction in the alkyl ketene dimer solution, and temperature of reaction is 65 ℃, and the reaction times is 0.8 hour; Be that 4% methyl-sulfate joins and carries out quaterisation in the reactor again with mass ratio, temperature of reaction is 76 ℃, and the time is 1.8 hours; Add glacial acetic acid at last and regulate after pH value is 5.0, stir that to add temperature down be 60 ℃ deionized water, get solids content and be 25% white emulsion.
Embodiment 4, at first 7% alkyl ketene dimer is joined in the dry reactor by mass ratio, and reactor is heated to 85 ℃, after making the alkyl ketene dimer fusion in the reactor, adding 25% tolylene diisocyanate, 51.26% relative molecular mass by mass ratio again is that the dibutyl tin laurate of 2000 polyester binary pure and mild 0.46% joins in the reactor and carried out polycondensation 1.5 hours at 85 ℃, forms the alkyl ketene dimer solution of base polyurethane prepolymer for use as; With mass ratio is that 13.28% N methyldiethanol amine joins and carries out chain extending reaction in the alkyl ketene dimer solution, and temperature of reaction is 70 ℃, and the reaction times is 1.2 hours; Be that 3% methyl-sulfate joins and carries out quaterisation in the reactor again with mass ratio, temperature of reaction is 72 ℃, and the time is 1.6 hours; Add glacial acetic acid at last and regulate after pH value is 5.5, stir that to add temperature down be 40 ℃ deionized water, get solids content and be 25% white emulsion.
Embodiment 5, at first 8% alkyl ketene dimer is joined in the dry reactor by mass ratio, and reactor is heated to 83 ℃, after making the alkyl ketene dimer fusion in the reactor, adding 28% tolylene diisocyanate, 46% relative molecular mass by mass ratio again is that the dibutyl tin laurate of 1000 polyether Glycols and 0.42% joins in the reactor and carried out polycondensation 1.2 hours at 83 ℃, forms the alkyl ketene dimer solution of base polyurethane prepolymer for use as; With mass ratio is that 13.58% N methyldiethanol amine joins and carries out chain extending reaction in the alkyl ketene dimer solution, and temperature of reaction is 67 ℃, and the reaction times is 1.0 hours; Be that 4% methyl-sulfate joins and carries out quaterisation in the reactor again with mass ratio, temperature of reaction is 75 ℃, and the time is 1.5 hours; Add glacial acetic acid at last and regulate after pH value is 6.5, stir that to add temperature down be 80 ℃ deionized water, get solids content and be 25% white emulsion.
Embodiment 6, at first 9% alkyl ketene dimer is joined in the dry reactor by mass ratio, and reactor is heated to 78 ℃, after making the alkyl ketene dimer fusion in the reactor, adding 26% tolylene diisocyanate, 48% relative molecular mass by mass ratio again is that the dibutyl tin laurate of 2000 polyester binary pure and mild 0.43% joins in the reactor and carried out polycondensation 2.5 hours at 78 ℃, forms the alkyl ketene dimer solution of base polyurethane prepolymer for use as; With mass ratio is that 13.57% N methyldiethanol amine joins and carries out chain extending reaction in the alkyl ketene dimer solution, and temperature of reaction is 58 ℃, and the reaction times is 1.4 hours; Be that 3% methyl-sulfate joins and carries out quaterisation in the reactor again with mass ratio, temperature of reaction is 68 ℃, and the time is 2.0 hours; Add glacial acetic acid at last and regulate after pH value is 5.7, stir that to add temperature down be 50 ℃ deionized water, get solids content and be 25% white emulsion.
Claims (7)
1, the preparation method of compound emulsion of dimmer of cation polyurethane and alkyl ketene is characterized in that:
1) at first 6.83～10.65% alkyl ketene dimers is joined in the dry reactor by mass ratio, and reactor is heated to 75～90 ℃, after making the alkyl ketene dimer fusion in the reactor, and then by mass ratio the dibutyl tin laurate of 25.63%～30% tolylene diisocyanate, 40～51.26% polyglycol and 0.40～0.47% is joined in the reactor and to carry out polycondensation 1.0～2.5 hours at 75～90 ℃, form the alkyl ketene dimer solution of base polyurethane prepolymer for use as;
2) be that 12.82～15.77% N methyldiethanol amine joins and carries out chain extending reaction in the alkyl ketene dimer solution with mass ratio, temperature of reaction is 55～70 ℃, and the reaction times is 0.5～1.5 hour;
3) be that 3.0～5.0% methyl-sulfates join and carry out quaterisation in the reactor again with mass ratio, temperature of reaction is between 65～80 ℃, and the time is 1.0～2.0 hours;
4) add glacial acetic acid at last and regulate after pH value is 4.5～6.5, stir that to add temperature down be 20-90 ℃ deionized water, get solids content and be 25% white emulsion.
2, the preparation method of compound emulsion of dimmer of cation polyurethane and alkyl ketene according to claim 1, it is characterized in that: said polyglycol is polyether Glycols or polyester diol, and the number average relative molecular mass of polyether Glycols is 1000 or 2000, and the number average relative molecular mass of polyester diol is 1000 or 2000.
3, the preparation method of compound emulsion of dimmer of cation polyurethane and alkyl ketene according to claim 1, it is characterized in that: at first 6.83% alkyl ketene dimer is joined in the dry reactor by mass ratio, and reactor is heated to 90 ℃, after making the alkyl ketene dimer fusion in the reactor, press the tolylene diisocyanate of mass ratio adding 30% again, 44.88% relative molecular mass is that the dibutyl tin laurate of 1000 polyether Glycols and 0.47% joins in the reactor and carried out polycondensation 1.0 hours at 90 ℃, forms the alkyl ketene dimer solution of base polyurethane prepolymer for use as; With mass ratio is that 12.82% N methyldiethanol amine joins and carries out chain extending reaction in the alkyl ketene dimer solution, and temperature of reaction is 55 ℃, and the reaction times is 0.5 hour; Be that 5% methyl-sulfate joins and carries out quaterisation in the reactor again with mass ratio, temperature of reaction is 65 ℃, and the time is 1.0 hours; Add glacial acetic acid at last and regulate after pH value is 4.5, stir that to add temperature down be 20 ℃ deionized water, get solids content and be 25% white emulsion.
4, the preparation method of compound emulsion of dimmer of cation polyurethane and alkyl ketene according to claim 1, it is characterized in that: at first 10.65% alkyl ketene dimer is joined in the dry reactor by mass ratio, and reactor is heated to 75 ℃, after making the alkyl ketene dimer fusion in the reactor, press the tolylene diisocyanate of mass ratio adding 25.63% again, 44.55% relative molecular mass is that the dibutyl tin laurate of 2000 polyether Glycols and 0.40% joins in the reactor and carried out polycondensation 1.8 hours at 75 ℃, forms the alkyl ketene dimer solution of base polyurethane prepolymer for use as; With mass ratio is that 15.77% N methyldiethanol amine joins and carries out chain extending reaction in the alkyl ketene dimer solution, and temperature of reaction is 60 ℃, and the reaction times is 1.5 hours; Be that 3% methyl-sulfate joins and carries out quaterisation in the reactor again with mass ratio, temperature of reaction is 80 ℃, and the time is 1.2 hours; Add glacial acetic acid at last and regulate after pH value is 6.0, stir that to add temperature down be 90 ℃ deionized water, get solids content and be 25% white emulsion.
5, the preparation method of compound emulsion of dimmer of cation polyurethane and alkyl ketene according to claim 1, it is characterized in that: at first 10% alkyl ketene dimer is joined in the dry reactor by mass ratio, and reactor is heated to 80 ℃, after making the alkyl ketene dimer fusion in the reactor, press the tolylene diisocyanate of mass ratio adding 30% again, 40% relative molecular mass is that the dibutyl tin laurate of 1000 polyester binary pure and mild 0.45% joins in the reactor and carried out polycondensation 2.3 hours at 80 ℃, forms the alkyl ketene dimer solution of base polyurethane prepolymer for use as; With mass ratio is that 15.55% N methyldiethanol amine joins and carries out chain extending reaction in the alkyl ketene dimer solution, and temperature of reaction is 65 ℃, and the reaction times is 0.8 hour; Be that 4% methyl-sulfate joins and carries out quaterisation in the reactor again with mass ratio, temperature of reaction is 76 ℃, and the time is 1.8 hours; Add glacial acetic acid at last and regulate after pH value is 5.0, stir that to add temperature down be 60 ℃ deionized water, get solids content and be 25% white emulsion.
6, the preparation method of compound emulsion of dimmer of cation polyurethane and alkyl ketene according to claim 1, it is characterized in that: at first 8% alkyl ketene dimer is joined in the dry reactor by mass ratio, and reactor is heated to 83 ℃, after making the alkyl ketene dimer fusion in the reactor, press the tolylene diisocyanate of mass ratio adding 28% again, 46% relative molecular mass is that the dibutyl tin laurate of 1000 polyether Glycols and 0.42% joins in the reactor and carried out polycondensation 1.2 hours at 83 ℃, forms the alkyl ketene dimer solution of base polyurethane prepolymer for use as; With mass ratio is that 13.58% N methyldiethanol amine joins and carries out chain extending reaction in the alkyl ketene dimer solution, and temperature of reaction is 67 ℃, and the reaction times is 1.0 hours; Be that 4% methyl-sulfate joins and carries out quaterisation in the reactor again with mass ratio, temperature of reaction is 75 ℃, and the time is 1.5 hours; Add glacial acetic acid at last and regulate after pH value is 6.5, stir that to add temperature down be 80 ℃ deionized water, get solids content and be 25% white emulsion.
7, the preparation method of compound emulsion of dimmer of cation polyurethane and alkyl ketene according to claim 1, it is characterized in that: at first 9% alkyl ketene dimer is joined in the dry reactor by mass ratio, and reactor is heated to 78 ℃, after making the alkyl ketene dimer fusion in the reactor, press the tolylene diisocyanate of mass ratio adding 26% again, 48% relative molecular mass is that the dibutyl tin laurate of 2000 polyester binary pure and mild 0.43% joins in the reactor and carried out polycondensation 2.5 hours at 78 ℃, forms the alkyl ketene dimer solution of base polyurethane prepolymer for use as; With mass ratio is that 13.57% N methyldiethanol amine joins and carries out chain extending reaction in the alkyl ketene dimer solution, and temperature of reaction is 58 ℃, and the reaction times is 1.4 hours; Be that 3% methyl-sulfate joins and carries out quaterisation in the reactor again with mass ratio, temperature of reaction is 68 ℃, and the time is 2.0 hours; Add glacial acetic acid at last and regulate after pH value is 5.7, stir that to add temperature down be 50 ℃ deionized water, get solids content and be 25% white emulsion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100430180A CN1298760C (en) | 2005-07-28 | 2005-07-28 | Method for preparing compound emulsion of dimmer of cation polyurethane and alkyl ketene |
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| CNB2005100430180A CN1298760C (en) | 2005-07-28 | 2005-07-28 | Method for preparing compound emulsion of dimmer of cation polyurethane and alkyl ketene |
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| CN1298760C true CN1298760C (en) | 2007-02-07 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101096829B (en) * | 2007-07-13 | 2010-08-04 | 天津科技大学 | Cation alkyl ketene dimer sizing agent and method for making same |
| CN108951285A (en) * | 2018-08-02 | 2018-12-07 | 宁波高新区诠宝绶新材料科技有限公司 | A kind of preparation method of Neutral Papermaking polymeric material |
| CN111593598B (en) * | 2020-04-13 | 2021-12-31 | 仙鹤股份有限公司 | Preparation method of artificial leather release base paper with uniform sizing |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01197513A (en) * | 1988-02-02 | 1989-08-09 | Seiko Kagaku Kogyo Co Ltd | Preparation of polyurethane resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01197513A (en) * | 1988-02-02 | 1989-08-09 | Seiko Kagaku Kogyo Co Ltd | Preparation of polyurethane resin |
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