CN105672033A - Modified PAE (polyamide epichlorohydrin resin) coating waterproof agent and preparation method thereof - Google Patents
Modified PAE (polyamide epichlorohydrin resin) coating waterproof agent and preparation method thereof Download PDFInfo
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- CN105672033A CN105672033A CN201610072571.5A CN201610072571A CN105672033A CN 105672033 A CN105672033 A CN 105672033A CN 201610072571 A CN201610072571 A CN 201610072571A CN 105672033 A CN105672033 A CN 105672033A
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- waterproof agent
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/16—Sizing or water-repelling agents
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Abstract
The invention relates to the field of coating waterproof agents, aims to solve the problems that the conventional PAE type waterproof agent has high cost, cannot have excellent water resistance and excellent printability simultaneously, has higher organo-chlorine residue content and the like, and provides a modified PAE (polyamide epichlorohydrin resin) waterproof agent and a preparation method thereof. The coating waterproof agent is a modified PAE aqueous solution with the solid content of 50%-60%, the mass fraction of organo-chlorine is 0.5% or lower, the pH value is 6-8, the viscosity is 200 mPa*s or lower, and the coating waterproof agent has the characteristics of environmental protection and higher water resistance of a coating.
Description
Technical field
The present invention relates to coating water-proofing agent field, be specifically related to a kind of modified PAE (wet reinforcing agent-polyamine epichlorohydrin resin) coated waterproof agent and preparation method thereof.
Background technology
Coating used by Paper Coating adds water-proofing agent, it is possible to improve the coating surface strength of paper, wet friction performance, printing adaptability, reduce the generation falling hair, dry linting phenomenon. Especially when being coated with paper for colored printing, coating needs through multiple tracks moistening, if coating surface strength is not enough, it is easy to causes hair, dry linting phenomenon, has a strong impact on printing effect, so water-proofing agent must be added in coating improve water-resistant coating energy. Coating coating water-proofing agent conventional at present mainly has amino resins, zirconates and polyamide polyureas epichlorohydrin resin three major types. Amino resins is generally Lauxite, melamine resin and modifier thereof, and the production cost of amino resins is low, and technique is simple, but the formaldehyde gas that amino resins has carcinogenecity discharges, and is eliminated gradually. What zirconates was conventional has zirconium carbonate ammonium, as coated waterproof agent, has that addition is few, the fireballing advantage of ripening, but, in use penetrating odor ammonia taste, unfavorable with the working environment of workman, meanwhile, zirconium metal is heavy metal, limits its use in the industry such as Nicotiana tabacum L., food. Polyamide polyureas epichlorohydrin resin has developed into the main flow of paint used for coating water repellent agent, its advantage with lower machine ripening, formaldehydeless release, but, it there is also some shortcomings part, viscosity stability is poor, resistance to water and printing adaptability can not be simultaneously excellent, and the residual organochlorine containing high level; Both 1,3-bis-chloro-2-propanol, 3-chlorine-1,2-propylene glycol, and the problem such as unreacted epoxychloropropane. Increasingly strict along with environmental protection requirement, people are also more and more higher to the requirement of paper paper product simultaneously, and the research of modified PAE water-proofing agent is increasingly subject to pay attention to.
Japanese documentation JP86-281127 discloses a kind of thermosetting resin product-polyamide carbamide resin, but experiments show that this product cationic bridging agent cationic is strong not, the ink absorption causing into paper is still not ideal enough, and product solid content is not high, and production cost is high.
Summary of the invention
Cost height is there is for solving existing PAE type water-proofing agent, resistance to water and printing adaptability can not be simultaneously excellent, and containing problems such as relatively high residue organochlorines, the present invention provides a kind of modified PAE water-proofing agent and preparation method thereof, this water-proofing agent has the feature of environmental protection, the water resistance of higher coating.
The present invention is achieved by the following technical solutions: a kind of modified PAE coated waterproof agent, described coated waterproof agent is solid content be 50%～60% modified polyamide epichlorohydrin resin aqueous solution, wherein organochlorine mass fraction is lower than 0.5%, and pH value 6～8, viscosity is less than 200mPa.s. The present invention has formaldehydeless release, feature without heavy metal element, ultralow content of organic chloride.
Described preparation method is following steps:
(1) in binary acid add polyamines polyene, 150～190 DEG C react 1～4 hour, reaction concurrently separate the water reacting generation in system;
Described polyamines polyene is selected from one or several in diethylenetriamine, triethylene tetramine, TEPA.
It is 1: 1～1.3 that described binary acid is selected from the mol ratio of one or several in malonic acid, succinic acid, 1,3-propanedicarboxylic acid, adipic acid, 1,5-pentanedicarboxylic acid., SA, binary acid and polyamines polyene, it is preferable that mol ratio is 1: 1.05.
(2) the adjustment reaction system solid content that then adds water is 30～60%, temperature 50～100 DEG C, then adds carbamide in system, reacts 2～6 hours at 90～110 DEG C;
The mol ratio of described carbamide and polyamines polyene is 1: 1～1.25, it is preferable that mol ratio is 1: 1.
(3) add epoxychloropropane and glycidyl ether, react 4～10 hours at 20～50 DEG C;
The mol ratio of described epoxychloropropane and polyamines polyene is 0.5～1: 1, it is preferable that mol ratio is 0.7: 1.
Described glycidyl ether is selected from 1,4-butanediol diglycidyl ether, polypropylene glycol diglycidyl ether, 1, one or more in 6-hexanediol diglycidyl ether, propanetriol-diglycidyl-ether, Ethylene glycol diglycidyl ether, trimethylolpropane glycidyl ether, the mol ratio of glycidyl ether and polyamines polyene is 0.5～1: 1, it is preferable that mol ratio is 0.8: 1.
(4) being eventually adding water-based isocyanate to react 2～4 hours, adjust the pH value of system to 6～8, the adjustment solid content that adds water is 50%～60%, obtains a kind of modified PAE coated waterproof agent after cooling.
One or more in watersoluble closed type isocyanates NX6035, water-based isocyanate firming agent 3100, watersoluble closed isocyanate curing agent Y-102 of described water-based isocyanate, the addition of water-based isocyanate is the 1%～10% of polyamines polyene weight, it is preferred to 5%. Reaction system of the present invention introduces isocyanate groups, the better cross-linking properties improving water-proofing agent.
As preferably, being the acid for adjusting pH of 10-30% by weight concentration, acid is selected from one or several in sulphuric acid, acetic acid, nitric acid, citric acid.
The modified PAE coated waterproof agent of one of the present invention contains substantial amounts of epoxide group and adhesive generation cross-linking and curing reaction, forms stable network structure, improves the water resistance of coating; Excellent performance of the present invention, can be applicable in Paper Coating, has broad application prospects.
Compared with prior art, the invention has the beneficial effects as follows:
(1) water-proofing agent of the present invention has formaldehydeless release, feature without heavy metal element, ultralow content of organic chloride;
(2) water-proofing agent of the present invention improves water resistance and the cross-linking properties of coating.
Detailed description of the invention
By the examples below the present invention is described in further detail, raw materials used all commercially available in embodiment.
Embodiment 1
1mol (146g) adipic acid is equipped with in the four-hole boiling flask of electric stirring, thermometer, condenser and water knockout drum, add diethylenetriamine 1.05mol (108.3g), open stirring, it is warming up to 160 DEG C to react 3 hours, the water generation reaction concurrently separated in system of reaction, is cooled to 100 DEG C, add 220 grams of water, regulating solid content is 50%, adds carbamide 0.9mol, react 3 hours at 100 DEG C in system;Add epoxychloropropane 0.6mol and glycerin diglycidyl ether 0.6mol, react 6 hours at 30 DEG C; Add 5 grams of watersoluble closed type isocyanates NX6035 to react 2 hours, with in the sulphuric acid that weight concentration is 15% and the pH value of system to 7.0, adding water to solid content is 55%, cooling, obtains modified PAE coated waterproof agent 1, and the viscosity of coated waterproof agent 1 is 50mPa.s.
Embodiment 2
1mol (118.09g) succinic acid is equipped with in the four-hole boiling flask of electric stirring, thermometer, condenser and water knockout drum, add diethylenetriamine 1.0mol (146.2g), open stirring, it is warming up to 150 DEG C to react 4 hours, the water generation reaction concurrently separated in system of reaction, is cooled to 80 DEG C, add 190 grams of water, regulating solid content is 54.5%, adds carbamide 1mol, react 6 hours at 90 DEG C in system; Add epoxychloropropane 0.5mol and Ethylene glycol diglycidyl ether 0.5mol, react 10 hours at 20 DEG C; Add 1.5 grams of watersoluble closed type isocyanates NX6035 to react 3 hours, with in the citric acid that weight concentration is 10% and the pH value of system to 8.0, adding water to solid content is 52%, cooling, obtaining modified PAE coated waterproof agent 2, the solution viscosity of coated waterproof agent 2 is 80mPa.s.
Embodiment 3
1mol malonic acid (104.06g) is equipped with in the four-hole boiling flask of electric stirring, thermometer, condenser and water knockout drum, add triethylene tetramine 1.0mol (146.2g), open stirring, it is warming up to 190 DEG C to react 1 hour, the water generation reaction concurrently separated in system of reaction, is cooled to 50 DEG C, add 270 grams of water, regulating solid content is 44%, adds carbamide 0.9mol, react 2 hours at 110 DEG C in system; Add epoxychloropropane 0.8mol and BDDE 0.8mol, react 4 hours at 50 DEG C; Add 14.6 grams of watersoluble closed isocyanate curing agent Y-102 to react 4 hours, with in the acetic acid that weight concentration is 30% and the pH value of system to 6.0, adding water to solid content is 60%, cooling, obtaining modified PAE coated waterproof agent 3, the viscosity of coated waterproof agent 3 is 100mPa.s.
Embodiment 4
1mol 1,3-propanedicarboxylic acid (130.1g) is equipped with in the four-hole boiling flask of electric stirring, thermometer, condenser and water knockout drum, add TEPA 1.1mol (189.31g), open stirring, it is warming up to 170 DEG C to react 2 hours, the water generation reaction concurrently separated in system of reaction, is cooled to 70 DEG C, add 280 grams of water, regulating solid content is 50.3%, adds carbamide 0.9mol, react 4 hours at 95 DEG C in system; Add epoxychloropropane 1.1mol and polypropylene glycol diglycidyl ether 1.1mol, react 8 hours at 40 DEG C; Add 6 grams of water-based isocyanate firming agent 3100 to react 2 hours, with in the nitric acid that weight concentration is 20% and the pH value of system to 7.0, adding water to solid content is 57%, cooling, obtains modified PAE coated waterproof agent 4, and the viscosity of coated waterproof agent 4 is 100mPa.s.
Test case
(1) experiment adopts the art post paperboard being not coated with as bodystock paper, uses the modified PAE coated waterproof agent 1～4 that embodiment 1～4 obtains to be coated, coating weight 30g/m2, put into 105 DEG C of oven for drying.
(2) coating pattern rolling condition: take the small-sized calender press polish of above-mentioned coating pattern once (0.4Mpa, 90 DEG C) respectively
(3) when constant temperature and humidity, pattern testing result is as shown in table 1:
Table 1:
As can be seen from the above table: the coated waterproof agent of the present invention, after coating, the properties of paper is all better than commercially available product PAPU and zirconium ammonium water-proofing agent, the paper of coating has the surface strength of excellence, wet attriting performance, glossiness, and meanwhile, coating water-proofing agent content of organic chloride of the present invention is ultralow.This coating water-proofing agent possesses wide application prospect.
Claims (10)
1. a modified PAE coated waterproof agent, it is characterised in that described coated waterproof agent is solid content be 50%～60% modified polyamide epichlorohydrin resin aqueous solution, wherein organochlorine mass fraction is lower than 0.5%, and pH value 6～8, viscosity is less than 200mPa.s.
2. the preparation method modifiying PAE coated waterproof agent as claimed in claim 1, it is characterised in that described preparation method is following steps:
(1) in binary acid add polyamines polyene, 150～190 DEG C react 1～4 hour, reaction concurrently separate the water reacting generation in system;
(2) the adjustment reaction system solid content that then adds water is 30～60%, temperature 50～100 DEG C, then adds carbamide in system, reacts 2～6 hours at 90～110 DEG C;
(3) add epoxychloropropane and glycidyl ether, react 4～10 hours at 20～50 DEG C;
(4) being eventually adding water-based isocyanate to react 2～4 hours, adjust the pH value of system to 6～8, the adjustment solid content that adds water is 50%～60%, obtains a kind of modified PAE coated waterproof agent after cooling.
3. the preparation method of a kind of modified PAE coated waterproof agent according to claim 2, it is characterised in that the polyamines polyene described in step (1) is selected from one or several in diethylenetriamine, triethylene tetramine, TEPA.
4. the preparation method of a kind of modified PAE coated waterproof agent according to Claims 2 or 3, it is characterized in that, it is 1: 1～1.3 that binary acid described in step (1) is selected from the mol ratio of one or several in malonic acid, succinic acid, 1,3-propanedicarboxylic acid, adipic acid, 1,5-pentanedicarboxylic acid., SA, binary acid and polyamines polyene.
5. the preparation method of a kind of modified PAE coated waterproof agent according to Claims 2 or 3, it is characterised in that the mol ratio of the carbamide described in step (2) and polyamines polyene is 1: 1～1.25.
6. the preparation method of a kind of modified PAE coated waterproof agent according to Claims 2 or 3, it is characterised in that in step (3), epoxychloropropane is 0.5～1: 1 with the mol ratio of polyamines polyene.
7. the preparation method of a kind of modified PAE coated waterproof agent according to Claims 2 or 3, it is characterized in that, glycidyl ether described in step (3) is selected from 1,4-butanediol diglycidyl ether, polypropylene glycol diglycidyl ether, 1, the mol ratio of one or more in 6-hexanediol diglycidyl ether, propanetriol-diglycidyl-ether, Ethylene glycol diglycidyl ether, trimethylolpropane glycidyl ether, glycidyl ether and polyamines polyene is 0.5～1: 1.
8. the preparation method of a kind of modified PAE coated waterproof agent according to claim 2, it is characterized in that, one or more in watersoluble closed type isocyanates NX6035, water-based isocyanate firming agent 3100, watersoluble closed isocyanate curing agent Y-102 of water-based isocyanate described in step (4), the addition of water-based isocyanate is the 1%～10% of polyamines polyene weight.
9. the preparation method of a kind of modified PAE coated waterproof agent according to claim 2, it is characterized in that, step (4) is the acid for adjusting pH of 10～30% by mass concentration, one or several in sulphuric acid, acetic acid, nitric acid, citric acid of acid.
10. a kind of modified PAE coated waterproof agent application on Paper Coating as defined in claim 1.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109208382A (en) * | 2018-11-07 | 2019-01-15 | 济宁明升新材料有限公司 | A kind of wet strengthening agents for papermaking and preparation method thereof |
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| JPH01190483A (en) * | 1988-01-27 | 1989-07-31 | Canon Inc | Material to be recorded |
| CN1168390A (en) * | 1996-04-12 | 1997-12-24 | 住友化学工业株式会社 | Water soluble resins and application thereof to paper coating |
| CN101403205A (en) * | 2008-11-13 | 2009-04-08 | 中南大学 | Coating water-repellent agent and preparation method thereof |
| CN103524708A (en) * | 2013-10-16 | 2014-01-22 | 上海东升新材料有限公司 | Preparation method of closed water-based polyurethane modified PAE (polyarylether) wet strength agent |
| CN104119824A (en) * | 2014-07-31 | 2014-10-29 | 3M创新有限公司 | Adhesive composition as well as retro-reflective material and preparation method thereof |
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2016
- 2016-02-01 CN CN201610072571.5A patent/CN105672033B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01190483A (en) * | 1988-01-27 | 1989-07-31 | Canon Inc | Material to be recorded |
| CN1168390A (en) * | 1996-04-12 | 1997-12-24 | 住友化学工业株式会社 | Water soluble resins and application thereof to paper coating |
| CN101403205A (en) * | 2008-11-13 | 2009-04-08 | 中南大学 | Coating water-repellent agent and preparation method thereof |
| CN103524708A (en) * | 2013-10-16 | 2014-01-22 | 上海东升新材料有限公司 | Preparation method of closed water-based polyurethane modified PAE (polyarylether) wet strength agent |
| CN104119824A (en) * | 2014-07-31 | 2014-10-29 | 3M创新有限公司 | Adhesive composition as well as retro-reflective material and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109208382A (en) * | 2018-11-07 | 2019-01-15 | 济宁明升新材料有限公司 | A kind of wet strengthening agents for papermaking and preparation method thereof |
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