CN1089956A - A kind of novel method for preparing the polyurethane-acrylate copolymer emulsion - Google Patents
A kind of novel method for preparing the polyurethane-acrylate copolymer emulsion Download PDFInfo
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- CN1089956A CN1089956A CN 93110541 CN93110541A CN1089956A CN 1089956 A CN1089956 A CN 1089956A CN 93110541 CN93110541 CN 93110541 CN 93110541 A CN93110541 A CN 93110541A CN 1089956 A CN1089956 A CN 1089956A
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- polyurethane
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- acrylate copolymer
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- copolymer emulsion
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Abstract
The present invention is a kind of novel method for preparing the polyurethane-acrylate copolymer emulsion, it is characterized in that with maleic anhydride being that the polyurethane-polyurea and the acrylic ester monomer of end group carries out emulsion copolymerization; And can soap be arranged or do not have the soap copolymerization with ordinary method.The polyurethane-acrylate multipolymer that newly makes has the good characteristic of urethane and polyacrylic resin concurrently, price is more cheap simultaneously, is widely applicable for coatings industry, leather industry, textile industry, building material industry, mechanical industry etc. and makes coating, tackiness agent and seal gum.
Description
The present invention relates to a kind of is the polyurethane-polyurea and the acrylic ester copolymerization of end group with maleic anhydride, the novel method of preparation polyurethane-acrylate copolymer emulsion.
Be widely used as the Emulsion acrylic resin of coating and tackiness agent, though many good characteristics are arranged.But there is hot sticky cold crisp in its glued membrane, and the shortcoming of organic solvent-resistant does not make its application be subjected to certain restriction.At present, the method for this thermoplastic acrylic resin of modification has three kinds: the one, and with the unsaturated monomer and the acrylate monomer copolymerization of band active group, to obtain the thermosetting resin of slight self-crosslinking.The 2nd, the method for employing blend method or additional crosslink agent.The 3rd, directly use the method for other macromolecular compound or monomer and acrylic resin grafting or copolymerization.
In the third method of modifying, the most prominent is polyurethane-acrylate multipolymer (being abbreviated as PU-A).Because PU-A has the good characteristic of urethane and polyacrylic ester concurrently, can coordinate the best method of material cost simultaneously again.Therefore, be described as third generation aqueous polyurethane.
The method for preparing the PU-A multipolymer has four kinds: the one, by vinylformic acid hydroxyalkyl acrylate and polyisocyanates reaction, make PU-A.The 2nd, by unsaturated poly-hydroxy or thiol group compound and polyisocyanates reaction, make PU-A.The 3rd, generate urethane by unsaturated isocyanate, with the Acrylic Acid Monomer copolymerization, make PU-A again.The 4th, generate unsaturated polyester urethane by unsaturated acid, with the Acrylic Acid Monomer copolymerization, make PU-A again.In these four kinds of methods, with the most use is first method.Be characterized in: the unsaturated link(age) reactive behavior height of acrylic acid hydroxy alkyl ester makes PU-A easily.But, the price height of this reactive monomer, toxicity is also bigger.What the 4th kind of method was with the most use is to generate unsaturated polyester urethane by maleic anhydride or fumaric acid, makes PU-A.This method compares with using the acrylic acid hydroxy alkyl ester method, the low price of reactive monomer, and toxicity is less, and has on polyurethane chain-COOH, the water-based PU-A of formation reaction self-crosslinking.But, the glued membrane vulcanization rate of the PU-A multipolymer that generates with this method is slower.Because during the preparation unsaturated polyester, polymerization temperature is higher, unsaturated link(age) easily goes to pot, but makes it to reduce with the probability of Acrylic Acid Monomer copolymerization, so practical few.
The objective of the invention is at above-mentioned situation, employing be that the inexpensive maleic anhydride that can gather materials on the spot is used as urethane and acrylic ester copolymer bridge.But, not by after generating unsaturated polyester urethane, again with acrylic ester copolymer, preparation PU-A.But generate maleic anhydride is the polyurethane-polyurea of end group, makes aqueous polyurethane with the alkali neutralization again, and then with the acrylate monomer copolymerization, make PU-A.
The manufacture craft process: the polyurethane-polyurea that uses among the present invention is the PAUR polyureas, or the polyether(poly)urethane polyureas, or (A) class of polyester polyethers mixed type polyurethane-polyurea (total be abbreviated as PU-U).
Adopt the reaction of (A) class and epihalohydrins, react with maleic anhydride again; Perhaps (A) class directly with the maleic anhydride reaction, and then neutralize with neutralizing agent, make with the maleic anhydride be end group polyurethane-polyurea (being abbreviated as PU-U-MAB) (B).
Neutralizing agent available hydrogen potassium oxide KoH, sodium hydroxide NaoH, ammoniacal liquor NH
4Inorganic bases such as oH, also available organic bases, as: Trimethylamine 99, triethylamine and thanomin and so on etc.
With maleic anhydride is that polyurethane-polyurea (B) and the acrylic monomer (C) of end group carries out emulsion copolymerization and add protective material, initiator, emulsifying agent, makes polyurethane-acrylate copolymer emulsion PU-A(D).Emulsifier-free emulsion polymerization can not add emulsifying agent.Monomer (C) is alkyl acrylate or alkyl methacrylate, perhaps acrylic acid epoxy ester, or methacrylic acid epoxy ester.Wherein alkyl is C
1～C
8The moieties of monohydroxy-alcohol, dibasic alcohol, trivalent alcohol and tetravalent alcohol.Other contain vinyl can with the monomer of acrylic acid or the like copolymerization, as: vinyl acetate between to for plastic, vinyl cyanide, acrylic amide, styrenic etc. all are suitable for well.
The monomer (B) and the amount ratio (C) that participate in copolyreaction among the present invention are: (B): (C)=1～99%: 99～1% Wt%(C) can be single acrylic monomer, also can be the acrylic monomer mixture.
In the letex polymerization of the present invention, be a kind of reaction type polyurethane, itself have certain emulsifying property with amophoteric surface active because participate in (B) of copolyreaction.Therefore, can carry out emulsifier-free emulsion polymerization.But also can add emulsifying agent by traditional letex polymerization.Aniorfic surfactant commonly used, as: sodium lauryl sulphate, Sodium dodecylbenzene sulfonate, petroleum sodium sulfonate etc.Nonionic surface active agent commonly used, as: the peregal class, Tween-60, tween-80, Arlacel-60, Arlacel-80 etc., general consumption is 1～10 Wt% of latex weight.Can select colloid protective agent for use in addition, as: polyvinyl alcohol, cellulose family, gelatin etc., consumption are 1～8 Wt% of latex weight.
The initiator of the emulsion copolymerization of using among the present invention is Potassium Persulphate commonly used, ammonium persulphate; Perhaps use redox initiator, the mol ratio that requires reductive agent/superoxide is less than 1.Initiator amount is for participating in 0.2～0.8% Wt% of comonomer.
The emulsion polymerization temperature is 30～100 ℃ among the present invention, and the reaction times is 3～2h(hour).
The PU-A multipolymer of the present invention's preparation has improved the hot sticky cold crisp and the not solvent-proof shortcoming of acrylic resin glued membrane significantly.At many industrial sectors such as leather, weaving, papermaking, building, machineries, can be widely used as coating, tackiness agent and sealing compound etc.
Below be specific embodiments of the invention:
1, polyurethane-acrylate copolymer p U-A preparation: agitator, reflux exchanger are being housed, dropping funnel, during one liter four-hole of temperature control unit burns also, use the seed dripping method, the emulsion copolymerization prescription is: maleic anhydride is that polyurethane-polyurea (the B)-200g/ acrylic ester monomer (C) of end group is a kind of mix monomer, and it consists of: methyl methacrylate (MMA)-30g/ vinylbenzene (St)-30g/ butyl acrylate (BA)-60g/ Propylene glycol monoacrylate (HPA)-4g.Emulsifying agent is: sodium lauryl sulphate (SLS)-1.5g and peregal (OP-10)-2g.Colloid is protected the expansion agent: polyvinyl alcohol (PVA-124) (5% aqueous solution)-210g.Distilled water-100g.Initiator is: (NH
4)
2S
2O
8-1.25g is dissolved in the water of 50g.Polymerization temperature is 85 ± 5 ℃, and polymerization time is 10h, makes the emulsion particle exquisiteness, room temperature storage still very stable PU-A copolymer emulsion (D) more than a year.
2, performance test: with (D) and commercially available acrylic resin hide finishes: soft-1, in-1 and the SB resin emulsion water on sheet glass the drying at room temperature film forming respectively.The glued membrane that makes is placed on the paper, puts into-30 ℃ of freezing 3h of water tank, put into 100 ℃ of baking ovens again and bake 1h.Experimental result is as shown in the table.
The cold-resistant hot comparison of copolymerization PU-A and vinylformic acid finishing agent film
| The film classification | PU-A | SB | In-1 | Soft-1 |
| Cold resistance | Flexibility is good | Split off | Split off | Split off |
| Thermotolerance | Flexibility is good | Be clamminess | Sticking paper | Sticking paper |
Claims (4)
1, a kind of novel method for preparing the polyurethane-acrylate copolymer emulsion is characterized in that with maleic anhydride being that polyurethane-polyurea (A) and the acrylic ester monomer (B) of end group carries out emulsion copolymerization.
2, the novel method of preparation polyurethane-acrylate copolymer emulsion according to claim 1, it is characterized in that polyurethane-polyurea (A) is meant: after polyester type, polyether-type or polyester polyether(poly)urethane polyureas and the epihalohydrins reaction, react with maleic anhydride again, perhaps direct and maleic anhydride reacts, with the alkali neutralization, make (A) then.
3, the novel method of preparation polyurethane-acrylate copolymer emulsion according to claim 1, it is characterized in that acrylic ester monomer (B) is meant: alkyl acrylate or epoxy ester, or alkyl methacrylate or epoxy ester, perhaps can with the acrylic ester monomer copolymerization other the band vinyl compound.
4, the novel method of preparation polyurethane-acrylate copolymer emulsion according to claim 1 is characterized in that emulsion copolymerization includes soap copolymerization and two kinds of no soap copolymerization, and two kinds of copolymerization all can be undertaken by acrylate conventional emulsions copolymerization method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93110541A CN1045971C (en) | 1993-01-19 | 1993-01-19 | Method for preparation of polyurethane acrylic ester copolymerized emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93110541A CN1045971C (en) | 1993-01-19 | 1993-01-19 | Method for preparation of polyurethane acrylic ester copolymerized emulsion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1089956A true CN1089956A (en) | 1994-07-27 |
| CN1045971C CN1045971C (en) | 1999-10-27 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93110541A Expired - Fee Related CN1045971C (en) | 1993-01-19 | 1993-01-19 | Method for preparation of polyurethane acrylic ester copolymerized emulsion |
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| CN (1) | CN1045971C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1098325C (en) * | 1999-12-07 | 2003-01-08 | 山东轻工业学院 | Adhesive for paint coating paper and its preparing process |
| CN100338111C (en) * | 2002-06-12 | 2007-09-19 | 中国科学院成都有机化学研究所 | Double-phobia polyurethane-polyacrylic ester microemulsion and preparation process thereof |
| CN100392017C (en) * | 2005-10-12 | 2008-06-04 | 中国化工建设总公司常州涂料化工研究院 | Acrylate polyurethane water-dispersed resin and its making method |
| CN101235195B (en) * | 2008-02-27 | 2010-06-02 | 烟台万华聚氨酯股份有限公司 | Cation water polyurethane/acrylic ester composite emulsion and preparation method thereof |
| CN101760158B (en) * | 2008-12-24 | 2012-02-01 | 四川汇利实业有限公司 | Alcohol-water type environmental-protection safety composite adhesive preparation method |
| CN101735389B (en) * | 2009-12-17 | 2012-02-08 | 华东理工大学 | Emulsion template method for preparing soap free hydrophilic polymer porous material |
| CN101921380B (en) * | 2010-02-05 | 2012-08-08 | 江苏工业学院 | Polyacrylate-urethane copolymer and preparation method thereof |
| CN104177586A (en) * | 2013-05-22 | 2014-12-03 | 罗门哈斯公司 | Polyurea macromer and latexes thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5614565A (en) * | 1979-07-13 | 1981-02-12 | Nitto Electric Ind Co Ltd | Self-adhesive for surface protecting film |
| CN1036404C (en) * | 1990-05-22 | 1997-11-12 | 中国兵器工业第五三研究所 | Polyurethane complementary networks adhesive and its making method |
-
1993
- 1993-01-19 CN CN93110541A patent/CN1045971C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1098325C (en) * | 1999-12-07 | 2003-01-08 | 山东轻工业学院 | Adhesive for paint coating paper and its preparing process |
| CN100338111C (en) * | 2002-06-12 | 2007-09-19 | 中国科学院成都有机化学研究所 | Double-phobia polyurethane-polyacrylic ester microemulsion and preparation process thereof |
| CN100392017C (en) * | 2005-10-12 | 2008-06-04 | 中国化工建设总公司常州涂料化工研究院 | Acrylate polyurethane water-dispersed resin and its making method |
| CN101235195B (en) * | 2008-02-27 | 2010-06-02 | 烟台万华聚氨酯股份有限公司 | Cation water polyurethane/acrylic ester composite emulsion and preparation method thereof |
| CN101760158B (en) * | 2008-12-24 | 2012-02-01 | 四川汇利实业有限公司 | Alcohol-water type environmental-protection safety composite adhesive preparation method |
| CN101735389B (en) * | 2009-12-17 | 2012-02-08 | 华东理工大学 | Emulsion template method for preparing soap free hydrophilic polymer porous material |
| CN101921380B (en) * | 2010-02-05 | 2012-08-08 | 江苏工业学院 | Polyacrylate-urethane copolymer and preparation method thereof |
| CN104177586A (en) * | 2013-05-22 | 2014-12-03 | 罗门哈斯公司 | Polyurea macromer and latexes thereof |
| CN104177586B (en) * | 2013-05-22 | 2019-07-12 | 罗门哈斯公司 | Polyureas macromonomer and its latex |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1045971C (en) | 1999-10-27 |
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