CN1546547A - Anion aromatic aqueous polyaminoester resin posterior chain extending method - Google Patents
Anion aromatic aqueous polyaminoester resin posterior chain extending method Download PDFInfo
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- CN1546547A CN1546547A CNA2003101126812A CN200310112681A CN1546547A CN 1546547 A CN1546547 A CN 1546547A CN A2003101126812 A CNA2003101126812 A CN A2003101126812A CN 200310112681 A CN200310112681 A CN 200310112681A CN 1546547 A CN1546547 A CN 1546547A
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- polyurethane resin
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Abstract
The invention relates to a positive ion aromatic aqueous polyaminoester resin posterior chain extending method which is characterized in that, on the basis of the line form or body form aromatic aqueous base polyurethane resin, dyadic or more amine is utilized for emulsion chain expansion. The solid content of the aqueous polyurethane resin obtained through the method according to the present invention is high, it also possesses good combination property and satisfactory environmental protection feature.
Description
Technical field
The present invention relates to be used for the back chain extension processing method of the aromatic waterborne polyurethane resin of coating, leather, tackiness agent, specifically the back chain extension processing method of cationic aromatic waterborne polyurethane resin.
Background technology
Waterborne polyurethane resin has good comprehensive performances because of it and the outstanding feature of environmental protection is widely used in many aspects such as building, automobile, house decoration, furniture, packing, printing, glass fibre, leather, daily necessities, artwork.At present, be divided into aliphatics and aromatic series two big classes from selected polyisocyanates kind, aliphatics waterborne polyurethane resin over-all properties is the ageing-resistant performance excellence particularly, but the price height, the needs of low consumption colony in being difficult to adapt to; The relative aliphatics waterborne polyurethane resin of aromatic waterborne polyurethane resin price is much lower, but over-all properties is relatively poor relatively, it is low particularly the domestic production amount to be accounted for absolute big ionic aromatic waterborne polyurethane resin solid content, degree of crosslinking is low, intensity, elasticity, water-fast, anti-solvent, chemical resistance is poor, usage quantity is big, these all make the use range of aromatic waterborne polyurethane resin be restricted, also make the level and the class of China's waterborne polyurethane resin product be difficult to improve, directly restricted the competitive power of homemade waterborne polyurethane resin and external like product.Therefore, improve the degree of crosslinking of waterborne polyurethane resin, improve the solid content of waterborne polyurethane resin, and then promote the class of China's waterborne polyurethane resin, just become the task of top priority to take part in international competition more widely.The present invention proposes just with this understanding.
Ionic aromatic waterborne polyurethane resin solid content is low, and the reason that degree of crosslinking is low is that the molecular weight that can not do when synthesizing waterborne polyurethane resin is too big, and degree of crosslinking is too high, otherwise it is soluble in water that urethane resin is difficult to.The present invention makes low molecule, low crosslinking degree even does not have crosslinked urethane resin high-loadly to dissolve in and give waterborne polyurethane resin very high degree of crosslinking in the water simultaneously by back chain extension technology, thereby improves the waterborne polyurethane resin good comprehensive performances.
Summary of the invention
The present invention aim to provide a kind of make low molecule, low crosslinking degree even do not have crosslinked urethane resin high-loadly to dissolve in give the very back chain extension processing method of the cationic aromatic waterborne polyurethane resin of high-crosslinking-degree of waterborne polyurethane resin in the water simultaneously.
The technical solution that realizes above-mentioned purpose is as follows:
1, the back chain extension processing method of cationic aromatic waterborne polyurethane resin, on the ionomeric basis of the aromatic urethane of obtaining, the ionomeric structure of described aromatic urethane is shown as follows:
R polyether-polyurethane in the formula (I); It is characterized in that: utilize the above amine of binary or binary that emulsion is carried out the back chain extension;
The concrete operations mode is to add the neutralizing agent neutralization under 0-20 ℃, 1400 rev/mins-2800 rev/mins of high-speed stirring conditions for the aromatic urethane ionomer with formula (I) adds high speed dispersor in temperature; Add the water dispersant that emulsifying water must be stable, under 0-20 ℃, 1400 rev/mins-2800 rev/mins of high-speed stirring conditions, add polyamine chain extension, linking agent again, polyurethane aqueous dispersion body is carried out chain extension and crosslinked, make the polyurethane molecular chain increase and increase degree of crosslinking simultaneously, stirred 1-10 minute, obtain waterborne polyurethane resin, precipitation just obtains the cationic aromatic waterborne polyurethane resin product of the chain extension of formula (II);
Described neutralizing agent is a Glacial acetic acid; Glacial acetic acid is 1-5% by weight add-on;
Water is 40-65% by weight add-on;
Described polyamine is the small molecules diamine, is enamine, is different fluorine that ketone diamines that add-on is 1-10% by weight.
2, according to the back chain extension processing method of 1 described cationic aromatic waterborne polyurethane resin: it is characterized in that: described small molecules diamine is quadrol, be propylene diamine.
3, according to the back chain extension processing method of 1 described cationic aromatic waterborne polyurethane resin: it is characterized in that: described enamine is a tetraethylene pentamine.
Existing waterborne polyurethane resin synthetic technology has two big classes, the one, the aliphatics waterborne polyurethane resin is synthetic, thereby in the chain extension process of back, there is not heat release because the aliphatic polyisocyante speed of response is slow and causes and poly-ly make that the aqueous polyurethane dispersion particle is excessive cruelly, produce layering.So the back chain extension of aliphatics waterborne polyurethane resin can carry out under normal temperature even 30 ℃ of-50 ℃ of conditions.What abroad adopt all is chain extension technology behind the aliphatics waterborne polyurethane resin, as USP:5,959,003 is exactly with the synthetic waterborne polyurethane resin of IPDI (isoflurane chalcone diisocyanate), what back chain extension was used is ethylene diamine, and product rub resistance number of times in toluene of this method preparation reaches 1700 times; JP:09,316,394 and WO:98 12,273 all be with 4, the 4-dicyclohexyl methane diisocyanate synthesizes waterborne polyurethane resin, with chain extension behind the hydrazine hydrate; JP:2000,136,369 usefulness IPDI synthesize the water-based polyester urethane resin, with chain extension behind the diethylenetriamine, its bonding strength is 5.5 kilograms/25mm, soaked in the water 24 hours and 80 ℃ of water in after the immersion, its bonding strength is respectively 1.9 kilograms/25mm and 1.0 kilograms/25mm.Here the subject matter of Cun Zaiing is aliphatic polyisocyante price height, be 8.5 ten thousand yuan/ton as the IPDI market value, and the TDI market value is 1.8 ten thousand yuan/ton.In China, performance is the one of the main reasons of considering, is price but people's emphasis considers, so the aliphatics waterborne polyurethane resin just is subjected to certain restriction in the market of China.The 2nd, the aromatic waterborne polyurethane resin is synthetic because the aromatic polyisocyanate speed of response is fast, very exothermic in the chain extension process of back and cause sudden and violent poly-, thereby make that the aromatic waterborne polyurethane dispersion particle is excessive, produce layering.So chain extension technology is synthesized and can't be used at the aromatic waterborne polyurethane resin behind the normal temperature of aliphatics waterborne polyurethane resin.Domestic aromatic waterborne polyurethane resin all be now when synthetic resins, just polyurethane molecular amount and degree of crosslinking are accomplished enough big after, dissolve in the water, because of considering the molten water conservancy project skill of resin, previous synthetic polyurethane molecular amount and degree of crosslinking just are subjected to certain restriction, final product just exists solid content low, the aqueous aromatic urethane emulsion content is many below 30% both at home and abroad at present, and how far over-all properties such as tensile strength, elasticity, adhesive power, water-fast, anti-solvent, chemical resistance etc. can not show a candle to imported product.As JP:10324,722, with the synthetic waterborne polyurethane resin of MDI (diphenylmethanediisocyanate), do not carry out back chain extension technology; CN 1335328, and the aromatic urethane emulsion is not carried out the back chain extension yet.This patent invention be exactly the general as above two aspects are in addition comprehensive, the aromatic waterborne polyurethane resin is carried out the back chain extension under certain condition, satisfied the requirement of domestic market simultaneously to the product price ratio.
The present invention is on original line style or build aromatic waterborne polyurethane resin basis, utilizes the above amine of binary or binary that emulsion is carried out the back chain extension and obtains.Its inventive point is: line style or weak crosslinked aqueous polyurethane ionomer are dissolved in a spot of water, because these molecular resin amounts are little, do not have crosslinked or degree of crosslinking very low, form stable water dispersion so can dissolve at an easy rate in the water, in stable water dispersion, add the amine linking agent, the polyurethane molecular chain is increased, simultaneously, the polyurethane molecular degree of crosslinking is increased, use the waterborne polyurethane resin solid content height of this kind method preparation, can reach 60%, the product tensile strength is big, good springiness, adhesive power is strong, water-fast, anti-solvent, chemical resistance is excellent, good combination property.
Embodiment
Below by embodiment the present invention is done to describe further.
Embodiment 1,
With polyether-type aromatic urethane ionomer (NCO% is 0.32%) 782 grams, structural formula is suc as formula (I), add in the 3000ml plum blossom bucket, insert under the high speed dispersor, add Glacial acetic acid under 800 rev/mins, the 5 ℃ conditions: 4.8 grams, reacted 45 seconds, add entry under 5 ℃: 270 grams, add tetraethylene pentamine after 60 seconds: 3.2 grams, 5 ℃ get polyaminoester emulsion behind stirring 10 clocks down, change the precipitation still over to, 55 ℃, 0.8MPa under slough acetone and promptly get the aromatic series cationic water polyurethane resin, structural formula is suc as formula (II).Product solid content: 60%; Tensile strength: 6.3Mpa; Stripping strength (180 °): 11.57N/cm; Activation temperature: 60 ℃.Be suitable as water-based and mould composite gum.
Embodiment 2,
With polyethers, polyhutadiene type aromatic urethane ionomer (NCO% is 0.37%) 804 grams, add in the 3000ml plum blossom bucket, insert under the high speed dispersor, add Glacial acetic acid under 800 rev/mins, the 5 ℃ conditions: 5.2 grams, reacted 45 seconds, add entry under 5 ℃: 346 grams, add your ketone diamines of different fluorine after 60 seconds: 10.6 grams, 5 ℃ stir down after 5 minutes polyaminoester emulsion, change the precipitation still over to, 55 ℃, slough acetone under the 0.8MPa and promptly get the aromatic series cationic water polyurethane resin.Product solid content: 40%; Tensile strength: 3.24Mpa; Hardness (Shao A) 48; Film water tolerance (25 ℃, 72 hours) no change; Elongation at break (20 ℃): 280%.Be suitable as the glass fibre collecting agent.
Embodiment 3,
With polyether-type aromatic urethane ionomer (NCO% is 0.23%) 802 grams, add in the 3000ml plum blossom bucket, insert under the high speed dispersor, add Glacial acetic acid under 800 rev/mins, the 5 ℃ conditions: 2.8 grams, reacted 40 seconds, add entry under 5 ℃: 330 grams, add quadrol after 60 seconds: 1.8 grams, 5 ℃ of following stirrings get polyaminoester emulsion after 5 minutes, change the precipitation still over to, 55 ℃, slough acetone under the 0.8MPa and promptly get the aromatic series cationic water polyurethane resin.Product solid content: 48%; Tensile strength: 0.8Mpa; Hardness (Shao A) 62; Film elongation 1500%.Be suitable as water-based leather potting resin.
Embodiment 4,
With polytetrahydrofuran aromatic urethane ionomer (NCO% is 0.62%) 802 grams, add in the 3000ml plum blossom bucket, insert under the high speed dispersor, add Glacial acetic acid under 800 rev/mins, the 5 ℃ conditions: 8.5 grams, reacted 45 seconds, add entry under 5 ℃: 260 grams, add your ketone diamines of different fluorine after 60 seconds: 9.7 grams, 5 ℃ stir down after 5 minutes polyaminoester emulsion, change the precipitation still over to, 55 ℃, slough acetone under the 0.8MPa and promptly get the aromatic series cationic water polyurethane resin.Product solid content: 60%; Tensile strength: 38.4Mpa; Hardness (Shao D) 66; Gloss (60 °) 98; Film water tolerance (25 ℃, 72 hours) no change; Film alcohol resistance (25 ℃, 48 hours) no change.Be suitable as water-based leatheroid light resin.
Embodiment 5,
With polycaprolactone aromatic urethane ionomer (NCO% is 0.73%) 808 grams, add in the 3000ml plum blossom bucket, insert under the high speed dispersor, add Glacial acetic acid under 800 rev/mins, the 5 ℃ conditions: 10.1 grams, reacted 30 seconds, add entry under 5 ℃: 265 grams, add your ketone diamines of different fluorine after 60 seconds: 8.8 grams, 5 ℃ stir down after 5 minutes polyaminoester emulsion, change the precipitation still over to, 55 ℃, slough acetone under the 0.8MPa and promptly get the aromatic series cationic water polyurethane resin.Product solid content: 60%; Tensile strength: 44.5Mpa; Elongation at break: 210%; Film water tolerance (100 ℃, 0.5 hour) no change; Be suitable as water-based leatheroid resin.
Claims (3)
1, the back chain extension processing method of cationic aromatic waterborne polyurethane resin, on the ionomeric basis of the aromatic urethane of obtaining, the ionomeric structure of described aromatic urethane is shown as follows:
R is a polyether-polyurethane in the formula (I); It is characterized in that: utilize the above amine of binary or binary that emulsion is carried out the back chain extension;
The concrete operations mode is to add the neutralizing agent neutralization under 0-20 ℃, 1400 rev/mins-2800 rev/mins of high-speed stirring conditions for the aromatic urethane ionomer with formula (I) adds high speed dispersor in temperature; Add emulsifying water, under 0-20 ℃, 1400 rev/mins-2800 rev/mins of high-speed stirring conditions, add polyamine chain extension, linking agent again, stirred 1-10 minute, and obtained waterborne polyurethane resin, precipitation just obtains the cationic aromatic waterborne polyurethane resin product of the chain extension of formula (II);
Described neutralizing agent is a Glacial acetic acid; Glacial acetic acid is 1-5% by weight add-on;
Water is 40-65% by weight add-on;
Described polyamine is the small molecules diamine, is enamine, is different fluorine that ketone diamines that add-on is 1-10% by weight.
2, the back chain extension processing method of cationic aromatic waterborne polyurethane resin according to claim 1: it is characterized in that: described small molecules diamine is quadrol, is propylene diamine.
3, the back chain extension processing method of cationic aromatic waterborne polyurethane resin according to claim 1: it is characterized in that: described enamine is a tetraethylene pentamine.
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| CNB2003101126812A CN100491434C (en) | 2003-12-16 | 2003-12-16 | Anion aromatic aqueous polyaminoester resin posterior chain extending method |
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| CNB2003101126812A CN100491434C (en) | 2003-12-16 | 2003-12-16 | Anion aromatic aqueous polyaminoester resin posterior chain extending method |
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| CN1546547A true CN1546547A (en) | 2004-11-17 |
| CN100491434C CN100491434C (en) | 2009-05-27 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100366818C (en) * | 2004-03-01 | 2008-02-06 | 卡尔弗罗伊登柏格两合公司 | Method for manufacturing light-proof leatheroid and leatheroid thereof |
| CN105153904A (en) * | 2015-10-26 | 2015-12-16 | 刘朝辉 | Polyurea protective coating and preparation method thereof |
| CN106986979A (en) * | 2017-04-13 | 2017-07-28 | 合肥科天水性科技有限责任公司 | A kind of synchronous chain extension preparation technology of cationic aromatic aqueous polyurethane |
| CN109679056A (en) * | 2018-11-14 | 2019-04-26 | 万华化学集团股份有限公司 | A kind of self-crosslinkable polyurethane-polyurea water dispersion and its preparation method and application |
| CN109957087A (en) * | 2017-12-26 | 2019-07-02 | 万华化学（宁波）有限公司 | A kind of cation type polyurethane-polyurea water dispersion and its preparation method and application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4742095A (en) * | 1985-07-25 | 1988-05-03 | Mobay Corporation | Continuous process for the production of aqueous polyurethane-urea dispersions |
| GB8524579D0 (en) * | 1985-10-04 | 1985-11-06 | Polyvinyl Chemicals Inc | Coating compositions |
-
2003
- 2003-12-16 CN CNB2003101126812A patent/CN100491434C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100366818C (en) * | 2004-03-01 | 2008-02-06 | 卡尔弗罗伊登柏格两合公司 | Method for manufacturing light-proof leatheroid and leatheroid thereof |
| CN105153904A (en) * | 2015-10-26 | 2015-12-16 | 刘朝辉 | Polyurea protective coating and preparation method thereof |
| CN106986979A (en) * | 2017-04-13 | 2017-07-28 | 合肥科天水性科技有限责任公司 | A kind of synchronous chain extension preparation technology of cationic aromatic aqueous polyurethane |
| CN109957087A (en) * | 2017-12-26 | 2019-07-02 | 万华化学（宁波）有限公司 | A kind of cation type polyurethane-polyurea water dispersion and its preparation method and application |
| CN109957087B (en) * | 2017-12-26 | 2021-02-02 | 万华化学（宁波）有限公司 | Cationic polyurethane-polyurea aqueous dispersion, preparation method and application thereof |
| CN109679056A (en) * | 2018-11-14 | 2019-04-26 | 万华化学集团股份有限公司 | A kind of self-crosslinkable polyurethane-polyurea water dispersion and its preparation method and application |
| CN109679056B (en) * | 2018-11-14 | 2021-06-25 | 万华化学集团股份有限公司 | Self-crosslinking polyurethane-polyurea water dispersion and preparation method and application thereof |
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Assignee: Anhui Anda-Huatai New Material Co., Ltd. Assignor: Anhui University Contract record no.: 2011340000306 Denomination of invention: Anion aromatic aqueous polyaminoester resin posterior chain extending method Granted publication date: 20090527 License type: Exclusive License Open date: 20041117 Record date: 20110811 |
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Granted publication date: 20090527 Termination date: 20171216 |