CN102516920A - Aqueous polyurethane adhesive and preparation method thereof - Google Patents
Aqueous polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN102516920A CN102516920A CN2011104114953A CN201110411495A CN102516920A CN 102516920 A CN102516920 A CN 102516920A CN 2011104114953 A CN2011104114953 A CN 2011104114953A CN 201110411495 A CN201110411495 A CN 201110411495A CN 102516920 A CN102516920 A CN 102516920A
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Abstract
The invention discloses an aqueous polyurethane adhesive and a preparation method thereof. The aqueous polyurethane adhesive comprises, by weight, 100 parts of polyester polyol, 30 parts of isocyanate, 7-8 parts of auxiliary agent and the balance of deionized water. The preparation method comprises steps of: dehydrating polyester polyol, adding isocyanate, dimethylolpropionic acid, trimethylol propane and N-methyl pyrrolidone and adding dropwise a catalyst to obtain a performed polymer; then adding acetone and triethylamine for neutralization into salt; dispersing the mixture into deionized water with high speed shearing and carrying out emulsification; adding ethene diamine for chain extension and steaming out acetone with reduced pressure. The method of the invention has a simple technology, is practical and employs self-made aromatic polyurethane polyol; an R value, namely a value of NCO / OH is controlled at 1.4, and an addition of the DMPA is 3.5%; and the prepared aqueous polyurethane adhesive has strong Initial adhesion and good stability.
Description
Technical field
The present invention relates to that a kind of tack is strong, stability water-based polyurethane adhesive and preparation method thereof preferably.
Background technology
At present, shoemaking and the employed polyurethane adhesive of Suitcases & Leatherware industry all are to use toluene, YLENE, crude cresylic acid, acetone, the allotment of butanone equal solvent to form.In use atmosphere is polluted, the mankind are formed potential harm, and inflammable and explosive.
Water-based polyurethane adhesive is basic medium with water, have do not fire, nontoxic, pollution-free and advantage such as binding property, film-forming properties, mechanical property be good preferably.The research and development of aqueous polyurethane has become the research direction of current polyurethane field, and it is used also more and more widely.
But it is the difficult point of aqueous polyurethane that present water-based polyurethane adhesive has stronger initial cohesiveness when requiring it to have preferably stability.The present invention obtains the high-performance water-based polyurethane tackiness agent in the hope of through improving technology and prescription.
Summary of the invention
The objective of the invention is to overcome the deficiency of existing water-based polyurethane adhesive, a kind of water-based polyurethane adhesive that better stability and better initial bonding strength are arranged is provided.
Another object of the present invention is to provide the preparation method that a kind of preparation technology is simple, be prone to the water-based polyurethane adhesive of enforcement.
The present invention realizes through following technical scheme:
Water-based polyurethane adhesive is characterized in that, counts by weight, comprises following component:
100 parts of polyester polyols;
30 parts of isocyanic ester;
7 ~ 8 parts of auxiliary agents;
All the other are deionized water;
Wherein, said auxiliary agent comprises dibutyl tin dilaurate DBTDL, dimethylol propionic acid DMPA, TriMethylolPropane(TMP) TMP, N-N-methyl 2-pyrrolidone N-NMP, quadrol EDA, triethylamine TEA, acetone;
Polyester polyol provided by the present invention is the mixture of any ratio of aromatic polyester divalent alcohol PAD, THF homopolymer divalent alcohol PTMG and poly adipate succinic acid ester PBA;
Isocyanic ester provided by the present invention is hexamethylene diisocyanate HDI, Toluene-2,4-diisocyanate, the mixture of one or both of 4-vulcabond TDI.
The molecular weight of the aromatic polyester divalent alcohol PAD that the present invention is used is 2004; Be to be prepared by following method: aromatic binary carboxylic acid such as phthalic anhydride, PA etc. are had in the reaction kettle of whisking appliance and condensing surface with divalent alcohol such as glycol ether DEG, 1,4-butyleneglycol etc. accurate the adding, and heat temperature raising also feeds N
2Protection rises to 170 ~ 230 ℃ of dehydration esterifications in temperature, speed, temperature and the reaction times of control water outlet, set acid number, hydroxyl value by the time, and vacuumize then, to obtain setting the polyester diol of molecular weight.
Because the aromatic urethane polyvalent alcohol is the polyvalent alcohol that contains aromatic nucleus, the electrostatic attraction of phenyl ring that cloud density is high and electron deficiency part has increased the interaction between the molecular chain, so the concatenation ability of gained aqueous polyurethane is also very strong.The hardness of same glued membrane also is higher with aromatic polyester divalent alcohol type synthetic urethane hardness, and it is the contribution that the inflexible phenyl ring is done glued membrane hardness.Therefore the present invention adopts homemade aromatic urethane polyvalent alcohol to mix use with THF homopolymer divalent alcohol PTMG and poly adipate succinic acid ester PBA, and the water-based polyurethane adhesive initial bonding strength for preparing is stronger.
The preparation method of water-based polyurethane adhesive is characterized in that: may further comprise the steps:
A, polyester polyol is added in the reaction kettle; 30min dewaters under 90 ~ 120 ℃; Be cooled to 80 ℃ and add isocyanic ester, dimethylol propionic acid, TriMethylolPropane(TMP) and N-N-methyl 2-pyrrolidone N-, drip the catalyzer dibutyl tin dilaurate, under nitrogen protection; Reach 0.1%, obtain performed polymer in 80 ~ 90 ℃ of reactions to-NCO amount;
Wherein, to account for the weight percent of isocyanic ester be 3.5% to the add-on of said dimethylol propionic acid;
It is NCO/OH value=1.4 that the add-on of said isocyanic ester should satisfy the R value, and-NCO is the NCO mole number, and-OH is a polyester polyols alcoholic extract hydroxyl group mole number;
B, be cooled to 60 ℃ and add in acetone and the triethylamine and salify;
C, under high speed shear, be distributed to and carry out emulsification in the deionized water then, add the quadrol chain extension, decompression at last steams acetone, promptly obtains the aqueous polyurethane sizing agent.
Preparing method provided by the present invention is polymerized with isocyanic ester by polyester polyol under given conditions; Introduce in the molecular chain as internal emulsifying agent with dimethylol propionic acid (DMPA), DMPA content directly influences the wetting ability that hydrophilic monomer influences aqueous polyurethane.The present invention is controlled at 3.5% with the add-on of dimethylol propionic acid DMPA, and DMPA is low excessively, and the wetting ability of tackiness agent particle is not enough, and particle can be reunited and produced deposition in storage process; DMPA is too high, but water-intake rate is high, and causes emulsion viscosity to climb easily.
Should to satisfy the R value be NCO/OH value=1.4 to the add-on of polyester polyol and isocyanic ester among the present invention, and when the R value increased, stripping strength was increase tendency earlier; Stripping strength is maximum when R value ratio reaches 1.4 left and right sides; Then further increase along with the R value and reduce, this is because NCO content increases, and hydrogen bond, polarity effect increase between the molecular chain; Cross-linking set between the molecule increases, so stripping strength increases.But when the R value further increased, hard segment content and interaction force increased the reactivity that can hinder molecular chain, and soft section molecular motion also receives hard section effect of contraction and increases, thereby makes the glue-line hardening, and molecular weight is also along with decline, and therefore its adhesiveproperties descends.When therefore R value ratio was 1.4 left and right sides, stripping strength can obtain peak.
The water-based polyurethane adhesive initial bonding strength that the present invention prepares is stronger, and stability is better, and its preparation technology is simple; Be prone to implement; The preparation process can not pollute and poison atmosphere, has the splendid feature of environmental protection, effectively improves Working environment and effectively protects HUMAN HEALTH.
Embodiment
Further specify the present invention through embodiment below, following examples are preferred implementation of the present invention, but embodiment of the present invention does not receive the restriction of following embodiment.
Embodiment 1
[preparation of aromatic polyester divalent alcohol]:
Aromatic binary carboxylic acid and divalent alcohol are joined by accurate measurement in the reaction kettle that has condensing surface and whisking appliance, and heat temperature raising also feeds N
2Protection rises to 170 ~ 230 ℃ of dehydration esterifications in temperature, speed, temperature and the reaction times of control water outlet, set acid number, hydroxyl value by the time, and vacuumize then, be 2004 aromatic polyester divalent alcohol to obtain molecular weight.
[preparation of water-based polyurethane adhesive] comprises following component by weight:
The mixture of aromatic polyester divalent alcohol (PAD), poly adipate succinic acid ester (PBA) and THF homopolymer divalent alcohol (PTMG): 100 parts;
Hexamethylene diisocyanate (HDI): 30 parts;
Auxiliary agent: 7 parts, comprise dibutyl tin dilaurate (DBTDL), TriMethylolPropane(TMP) (TMP), dimethylol propionic acid (DMPA), quadrol (EDA), triethylamine (TEA), N-N-methyl 2-pyrrolidone N-(NMP), acetone;
All the other are deionized water: 200 parts.
Concrete preparation method is following: in the reaction kettle that whisking appliance, reflux condensing tube, nitrogen turnover pipe are housed, add polyester polyol, 30min dewaters under 90 ~ 120 ℃; Be cooled to and add dimethylol propionic acid, TriMethylolPropane(TMP), N-Methyl pyrrolidone, hexamethylene diisocyanate about 80 ℃; Wherein, the weight percent that the add-on of dimethylol propionic acid accounts for isocyanic ester is 3.5%, drips the catalyzer dibutyl tin dilaurate; Under nitrogen protection; Reaction to-NCO content reaches 0.1% under 80 ~ 90 ℃ temperature, and control NCO/OH value=1.4 obtain performed polymer; Be cooled to the acetone and the triethylamine of 60 ℃ of addings, in and 15min, in system, add deionized water, dispersion and emulsion under high speed shear adds quadrol then, chain extending reaction 15min, at last the decompression steam acetone, just obtain water-based polyurethane adhesive.
Embodiment 2
By weight, comprise following component:
The mixture of aromatic polyester divalent alcohol (PAD), poly adipate succinic acid ester (PBA) and THF homopolymer divalent alcohol (PTMG): 100 parts;
Toluene-2,4-diisocyanate, 4-vulcabond (TDI): 30 parts;
Auxiliary agent: 8 parts, comprise dibutyl tin dilaurate (DBTDL), TriMethylolPropane(TMP) (TMP), dimethylol propionic acid (DMPA), quadrol (EDA), triethylamine (TEA), N-N-methyl 2-pyrrolidone N-(NMP), acetone;
All the other are deionized water: 200 parts;
Its preparation method is with embodiment 1.
Claims (4)
1. water-based polyurethane adhesive is characterized in that, counts by weight, comprises following component:
100 parts of polyester polyols;
30 parts of isocyanic ester;
7 ~ 8 parts of auxiliary agents;
All the other are deionized water;
Wherein, said auxiliary agent comprises dibutyl tin dilaurate, dimethylol propionic acid, TriMethylolPropane(TMP), N-N-methyl 2-pyrrolidone N-, quadrol, triethylamine, acetone;
Said polyester polyol is the mixture of any ratio of aromatic polyester divalent alcohol PAD, THF homopolymer divalent alcohol PTMG and poly adipate succinic acid ester PBA;
Said isocyanic ester is hexamethylene diisocyanate HDI, Toluene-2,4-diisocyanate, the mixture of one or both of 4-vulcabond TDI.
2. water-based polyurethane adhesive according to claim 1 is characterized in that: the molecular weight of said aromatic polyester divalent alcohol PAD is 2004.
3. water-based polyurethane adhesive according to claim 2 is characterized in that: said aromatic polyester divalent alcohol PAD is prepared by following method: aromatic binary carboxylic acid and divalent alcohol are added in the reaction kettle, and heat temperature raising also feeds N
2Protection rises to 170 ~ 230 ℃ of dehydration esterifications at warm ℃, speed, temperature and the reaction times of control water outlet, set acid number, hydroxyl value by the time, and vacuumize then, to obtain setting the polyester diol of molecular weight.
4. the preparation method of the described water-based polyurethane adhesive of claim 1 is characterized in that: may further comprise the steps:
A, polyester polyol is added in the reaction kettle; 30min dewaters under 90 ~ 120 ℃; Be cooled to 80 ℃ and add isocyanic ester, dimethylol propionic acid, TriMethylolPropane(TMP) and N-N-methyl 2-pyrrolidone N-, drip the catalyzer dibutyl tin dilaurate, under nitrogen protection; Reach 0.1%, obtain performed polymer in 80 ~ 90 ℃ of reactions to-NCO amount;
Wherein, to account for the isocyanic ester weight percent be 3.5% to the add-on of said dimethylol propionic acid;
It is NCO/OH value=1.4 that the add-on of said isocyanic ester should satisfy the R value, and-NCO is the NCO mole number, and-OH is a polyester polyols alcoholic extract hydroxyl group mole number;
B, be cooled to 60 ℃ and add in acetone and the triethylamine and salify;
C, under high speed shear, be distributed to and carry out emulsification in the deionized water then, add the quadrol chain extension, decompression at last steams acetone, promptly obtains the aqueous polyurethane sizing agent.
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| CN2011104114953A CN102516920A (en) | 2011-12-12 | 2011-12-12 | Aqueous polyurethane adhesive and preparation method thereof |
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| CN2011104114953A CN102516920A (en) | 2011-12-12 | 2011-12-12 | Aqueous polyurethane adhesive and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746818A (en) * | 2012-07-26 | 2012-10-24 | 南京工业大学 | Waterborne polyurethane material and preparation method thereof |
| CN104497949A (en) * | 2014-12-02 | 2015-04-08 | 佛山铭乾科技有限公司 | Preparation method of novel high-solid-content waterborne polyurethane adhesive for shoes |
| CN105544247A (en) * | 2016-01-25 | 2016-05-04 | 苏州印丝特纺织数码科技有限公司 | Printing adhesive for digital printing and preparation method thereof |
| CN107488432A (en) * | 2017-08-22 | 2017-12-19 | 安徽艾米伦特建材科技有限公司 | Epoxidation modification polyurethane adhesive and preparation method thereof |
| CN111440602A (en) * | 2020-03-31 | 2020-07-24 | 安徽中科日升科技有限公司 | Thixotropic oil-based drilling fluid |
| CN112143435A (en) * | 2020-09-25 | 2020-12-29 | 烟台斯普瑞电子材料有限公司 | Hot-melt reaction type polyurethane adhesive for compounding electronic nylon film |
| CN112309703A (en) * | 2020-11-03 | 2021-02-02 | 安徽智磁新材料科技有限公司 | Solidification method of nanocrystalline magnetic core |
| CN112851905A (en) * | 2021-01-11 | 2021-05-28 | 吉林天泽二氧化碳科技有限公司 | High-temperature-resistant water polyurethane, preparation method thereof, water-based polyurethane adhesive and preparation method thereof |
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| CN101544880A (en) * | 2009-03-12 | 2009-09-30 | 中山市康和化工有限公司 | Adhesive for soft package compound and preparation method thereof |
| WO2010118948A1 (en) * | 2009-04-14 | 2010-10-21 | Basf Se | Adhesive made of polymers having crystalline domains, amorphous polyurethane and silane compounds |
| CN102102005A (en) * | 2010-12-13 | 2011-06-22 | 嘉兴禾欣化学工业有限公司 | Preparation method of environmentally-friendly aqueous polyurethane adhesive |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101544880A (en) * | 2009-03-12 | 2009-09-30 | 中山市康和化工有限公司 | Adhesive for soft package compound and preparation method thereof |
| WO2010118948A1 (en) * | 2009-04-14 | 2010-10-21 | Basf Se | Adhesive made of polymers having crystalline domains, amorphous polyurethane and silane compounds |
| CN102102005A (en) * | 2010-12-13 | 2011-06-22 | 嘉兴禾欣化学工业有限公司 | Preparation method of environmentally-friendly aqueous polyurethane adhesive |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746818A (en) * | 2012-07-26 | 2012-10-24 | 南京工业大学 | Waterborne polyurethane material and preparation method thereof |
| CN102746818B (en) * | 2012-07-26 | 2013-12-25 | 南京工业大学 | Waterborne polyurethane material and preparation method thereof |
| CN104497949A (en) * | 2014-12-02 | 2015-04-08 | 佛山铭乾科技有限公司 | Preparation method of novel high-solid-content waterborne polyurethane adhesive for shoes |
| CN105544247A (en) * | 2016-01-25 | 2016-05-04 | 苏州印丝特纺织数码科技有限公司 | Printing adhesive for digital printing and preparation method thereof |
| CN105544247B (en) * | 2016-01-25 | 2018-10-12 | 吴雨潞 | A kind of printing adhesive and preparation method thereof for digit printing |
| CN107488432A (en) * | 2017-08-22 | 2017-12-19 | 安徽艾米伦特建材科技有限公司 | Epoxidation modification polyurethane adhesive and preparation method thereof |
| CN111440602A (en) * | 2020-03-31 | 2020-07-24 | 安徽中科日升科技有限公司 | Thixotropic oil-based drilling fluid |
| CN111440602B (en) * | 2020-03-31 | 2022-11-15 | 安徽中科日升科技有限公司 | Thixotropic oil-based drilling fluid |
| CN112143435A (en) * | 2020-09-25 | 2020-12-29 | 烟台斯普瑞电子材料有限公司 | Hot-melt reaction type polyurethane adhesive for compounding electronic nylon film |
| CN112309703A (en) * | 2020-11-03 | 2021-02-02 | 安徽智磁新材料科技有限公司 | Solidification method of nanocrystalline magnetic core |
| CN112851905A (en) * | 2021-01-11 | 2021-05-28 | 吉林天泽二氧化碳科技有限公司 | High-temperature-resistant water polyurethane, preparation method thereof, water-based polyurethane adhesive and preparation method thereof |
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Application publication date: 20120627 |