CN1687191A - Aqucous polyurethane modified from vinyl resin possessing structure of bisphenol A and its preparing process - Google Patents
Aqucous polyurethane modified from vinyl resin possessing structure of bisphenol A and its preparing process Download PDFInfo
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- CN1687191A CN1687191A CN 200510038680 CN200510038680A CN1687191A CN 1687191 A CN1687191 A CN 1687191A CN 200510038680 CN200510038680 CN 200510038680 CN 200510038680 A CN200510038680 A CN 200510038680A CN 1687191 A CN1687191 A CN 1687191A
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Abstract
The present invention relates to a vinyl resin modified water polyurethane with bisphenol A structure and its preparation method. It is characterized by that its raw materal includes polyurethane resin with hydrophilicity and terminated bouble-bond, vinyl resin with bisphenol A structure and free radical polymerization initiator, and it is made up by adopting the following processes; fully mixing the above-mentioned two resins, dispersing distilled water to form uniform emulsion, drop-adding initiator to make polymerization reaction so as to obtain the invented product.
Description
Technical field:
The present invention relates to technology with epoxy resin modified aqueous polyurethane.
Background technology:
Aqueous polyurethane is with the new polyurethane system of water to replace organic solvent as dispersion medium, can be widely used in aspects such as coating, tackiness agent, hide finishes, fabric finishing agent.Because the existence of hydrophilic radical and the some shortcomings part of resin itself cause it to show the some shortcomings part at aspects such as water tolerance, solvent resistance, weathering resistancies in the polyurethane macromolecular, have influenced the use range of this series products to a certain extent.High-performances such as Resins, epoxy is well bonding owing to having, resistance to chemical attack, high strength, be usually used in the modification of polyurethane material, but, because the β-C in the epoxide group is subjected to nucleophilic reagents such as triethylamine, hydroxyl, water, Sauerstoffatom is subjected to proton or Lewis acid electrophilic reagent attack generation ring-opening reaction, cause the emulsion package stability relatively poor, therefore when directly using the epoxy resin modified aqueous polyurethane resin, be restricted to a great extent.
Summary of the invention:
The present invention is for solving above-mentioned existing in prior technology problem, a kind of Aqucous polyurethane modified from vinyl resin with structure of bisphenol A and preparation method thereof is provided, further improve stability on the basis of improving its over-all properties.
The technical scheme that technical solution problem of the present invention is adopted is:
The present invention has the Aqucous polyurethane modified from vinyl resin of structure of bisphenol A, and raw material by weight consists of:
The end capped urethane resin PUV:100 of keys possess hydrophilic property, two,
Vinylite with structure of bisphenol A: 5-50,
Radical polymerization initiator: 0.03-0.3,
Distilled water: 160-250.
The preparation method that the present invention has the Aqucous polyurethane modified from vinyl resin of structure of bisphenol A adopts polymerization technique, the Vinylite that will have a structure of bisphenol A mixes fully with urethane resin PUV after, disperse to form uniform emulsion with distilled water, the dropping initiator carries out polyreaction and makes.
The present invention utilizes the oxidation-reduction Raolical polymerizable, employing has the Aqucous polyurethane modified from vinyl resin resin of structure of bisphenol A, be introduced into possess hydrophilic property, on the end capped urethane resin PUV of the two keys molecular chain, in the structure of bisphenol A of having introduced Resins, epoxy, avoid Resins, epoxy to be directly used in the deficiency of waterborne polyurethane modified back emulsion package stability difference again, reached the purpose of comprehensive raising aqueous polyurethane emulsion performance.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the invention solves conventional Resins, epoxy and be directly used in the deficiency that aqueous polyurethane is reelected back emulsion package stability difference.
2, the invention solves that aqueous polyurethane is water-fast, the difficult problem of poor solvent resistance.
3, the present invention preferably resolves the relatively poor problem of consistency between Resins, epoxy and the urethane resin.
Embodiment:
Aqucous polyurethane modified from vinyl resin raw material by weight with structure of bisphenol A consists of:
The end capped urethane resin PUV:100 of keys possess hydrophilic property, two,
Vinylite with structure of bisphenol A: 5-50,
Radical polymerization initiator: 0.03-0.3.
Distilled water: 160-250
In concrete the enforcement, the end capped urethane resin PUV of keys possess hydrophilic property, two is that the macromole and the polyisocyanates that contain two or more active hydrogen functional groups pass through progressively addition polymerization, is synthesized through chain extension, salify step.Wherein, the macromole that contains two or more active hydrogen functional groups is the polyether Glycols of molecular weight between 400-4000, or the polyester diol of molecular weight between 400-4000, or the mixture between them.As mixture, can be the mixture of molecular weight different polyether Glycols between 400-4000, can be the mixture of the different polyester diol of molecular weight between 400-4000, also can be the mixture of polyether Glycols and polyester diol.
Vinylite with structure of bisphenol A is to be formed by the prepared in reaction between carboxyl and the epoxide group between acrylic acid or the like small molecules and the Resins, epoxy.Wherein, the acrylic acid or the like small molecules is a vinylformic acid, or acrylic acid derivative, or their mixture; Described Resins, epoxy is that oxirane value is a 0.2-0.51 Resins, epoxy, or their mixture.
Radical polymerization initiator is the ammonium persulfate-sodium bisulfite compound system.
The preparation method:
Adopt polymerization technique, the Vinylite that will have a structure of bisphenol A mixes fully with urethane resin PUV after, disperse the uniform emulsion of formation with distilled water, the dropping initiator is finished polyreaction.Be prepared as follows:
Preparation with Vinylite of structure of bisphenol A:
Resins, epoxy is sloughed small molecular weight impurity under 100 ℃, 0.1MPa condition; Add acrylic acid or the like small molecules at 1: 2 according to mol ratio, reaction is 6 hours under 100 ℃ of conditions; Unreacted residual acrylic acid or the like small molecules is sloughed in decompression;
The preparation of the end capped urethane resin PUV of keys possess hydrophilic property, two:
Two or more active hydrogen functional group macromole are cooled to 75 ℃ in dehydration under 120 ℃, 0.1MPa condition after 1 hour, added polyisocyanates and tin class catalyst reaction 30 minutes; Adding is dissolved hydrophilic monomer dihydroxymethyl vinylformic acid completely with dimethyl formamide, continues reaction and adds small molecule chain extender after 30 minutes, and adding Hydroxyethyl acrylate after being cooled to 60 ℃ after 60 minutes continues reaction 3 hours; Add salt forming agent after being cooled to 25 ℃;
Preparation with Aqucous polyurethane modified from vinyl resin of structure of bisphenol A:
The Vinylite that will have structure of bisphenol A joins in the middle of two end capped waterborne polyurethane resin PUV of key, under 45 ℃ of conditions, fully mixed 30-60 minute, add distilled water after reducing to room temperature, be warming up to 40-65 ℃ and drip initiator after being uniformly dispersed, promptly finish through 4-8 hour polyreaction.
The preparation method 1:
1, Vinylite synthetic that has structure of bisphenol A:
100 gram epoxy resin E-44s after sloughing small molecular weight impurity under 100 ℃, 0.1MPa condition, are added 63.36 gram vinylformic acid according to mol ratio at 1: 2, and reaction is 6 hours under 100 ℃ of conditions, and unreacted residual vinylformic acid small molecules is sloughed in decompression.
2, possess hydrophilic property, the end capped urethane resin PUV of two keys synthetic:
Being 1000 polyoxypropyleneglycol under 120 ℃, 0.1MPa condition with 40 grams, molecular weight, dehydration was cooled to 75 ℃ after 1 hour, add 22.5 grams 2,4-tolylene diisocyanate and 0.05 gram dibutyl tin laurate (catalyzer), react to add after 30 minutes and dissolve complete dimethylol propionic acid 7.6 grams with dimethyl formamide, continue reaction and add chainextender 1 after 30 minutes, 4-butyleneglycol 2.0 grams, react and add Hydroxyethyl acrylate 2.5 grams after being cooled to 60 ℃ after 60 minutes, react and be cooled to 25 ℃ after 3 hours, adding salt forming agent triethylamine 5 grams;
3, the preparation that has the Vinylite modified waterborne polyurethane of structure of bisphenol A
The Vinylite that 15 grams are had a structure of bisphenol A joins in the middle of the 100 gram PUV resins, under 45 ℃ of conditions, fully mix, be cooled to 25 ℃ and add water-dispersion, be warming up to 45 ℃ and the slow oxidation-reduction initiators that drip behind the formation homogeneous latex emulsion, polyreaction was finished in 6 hours.
By table 1 as seen, adopt the epoxy resin modified aqueous polyurethane resin with structure of bisphenol A of present method preparation, have water-fast preferably, anti-solvent, mechanical property, have very good emulsion package stability simultaneously, successfully solved the deficiency of direct use epoxy resin modified aqueous polyurethane resin emulsion package stability difference.
The preparation method 2:
Present method is identical with aforesaid method one, and different is when preparation has the Vinylite of structure of bisphenol A, and what the acrylic acid or the like small molecules adopted is methacrylic acid.
The preparation method 3:
Present method is identical with aforesaid method one, and different is when preparation has the Vinylite of structure of bisphenol A, and Resins, epoxy adopts Resins, epoxy E-51.
Preparation method 2, preparation method 3 are similar on performance to aforesaid method 1 prepared waterborne polyurethane resin.
The preparation method 4: present method is identical with aforesaid method 1, the molecular weight that the polyoxypropyleneglycol that different use when the end capped urethane resin PUV of preparation possess hydrophilic property, two key adopts is 2000, and the waterborne polyurethane resin that this method makes has mechanical property preferably.
| Film | Tensile strength/Mpa | Elongation at break/% | Water-intake rate/% | Solvent resistance | Package stability (my god) in 50 ℃ of baking ovens |
| Method one | ????21.21 | ????420 | ????8.0 | Well | Greater than 60 days |
| Method two | ????21.17 | ????452 | ????8.3 | Well | Greater than 60 days |
| Method three | ????22.02 | ????430 | ????8.7 | Well | Greater than 60 days |
| Method four | ????25.35 | ????450 | ????6.0 | Well | Greater than 60 days |
| Method five | ????24.73 | ????360 | ????4.2 | Excellent | 40 days |
The preparation method five:
Present method is identical with aforesaid method one, different is is that the Vinylite that 30 grams have a structure of bisphenol A is joined in the middle of the PUV resins of 100 grams when implementation step (3), the waterborne polyurethane resin that this method makes has water-fast preferably, solvent resistance, but the emulsion package stability descends.
Claims (8)
1, the Aqucous polyurethane modified from vinyl resin that has structure of bisphenol A is characterized in that raw material by weight consists of:
The end capped urethane resin PUV:100 of keys possess hydrophilic property, two,
Vinylite with structure of bisphenol A: 5-50,
Radical polymerization initiator: 0.03-0.3,
Distilled water: 160-250.
2, modified aqueous polyurethane according to claim 1, it is characterized in that described possess hydrophilic property, the end capped urethane resin PUV of two keys contains the macromole of two or more active hydrogen functional groups and polyisocyanates by progressively addition polymerization, and synthesized through chain extension, salify.
3, modified aqueous polyurethane according to claim 2, it is characterized in that the described macromole that contains two or more active hydrogen functional groups is the polyether Glycols of molecular weight between 400-4000, or the polyester diol of molecular weight between 400-4000, or their mixture.
4, modified aqueous polyurethane according to claim 1 is characterized in that described Vinylite with structure of bisphenol A is to be formed by the prepared in reaction between carboxyl and the epoxide group between acrylic acid or the like small molecules and the Resins, epoxy.
5, modified aqueous polyurethane according to claim 4 is characterized in that described acrylic acid or the like small molecules is a vinylformic acid, or acrylic acid derivative, or their mixture; Described Resins, epoxy is that oxirane value is a 0.2-0.51 Resins, epoxy, or their mixture.
6, modified aqueous polyurethane according to claim 1 is characterized in that described radical polymerization initiator is the ammonium persulfate-sodium bisulfite compound system.
7, the preparation method of the described modified aqueous polyurethane of claim 1, it is characterized in that adopting polymerization technique, the Vinylite that will have a structure of bisphenol A mixes fully with urethane resin PUV after, disperse to form uniform emulsion, drip initiator and carry out polyreaction and make with distilled water.
8, preparation method according to claim 7 is characterized in that:
A, have the preparation of the Vinylite of structure of bisphenol A: Resins, epoxy is sloughed small molecular weight impurity under 100 ℃, 0.1MPa condition; Add acrylic acid or the like small molecules at 1: 2 according to mol ratio, reaction is 6 hours under 100 ℃ of conditions; Unreacted residual acrylic acid or the like small molecules is sloughed in decompression;
The preparation of the end capped urethane resin PUV of key b, possess hydrophilic property, two: two or more active hydrogen functional group macromole are cooled to 75 ℃ in dehydration under 120 ℃, 0.1MPa condition after 1 hour, added polyisocyanates and tin class catalyst reaction 30 minutes; Adding is dissolved hydrophilic monomer dihydroxymethyl vinylformic acid completely with dimethyl formamide, continues reaction and adds small molecule chain extender after 30 minutes, and adding Hydroxyethyl acrylate after being cooled to 60 ℃ after 60 minutes continues reaction 3 hours; Add salt forming agent after being cooled to 25 ℃;
C, have the preparation of the Aqucous polyurethane modified from vinyl resin of structure of bisphenol A: the Vinylite that will have structure of bisphenol A joins in the middle of two end capped waterborne polyurethane resin PUV of key, under 45 ℃ of conditions, fully mixed 30-60 minute, add distilled water after reducing to room temperature, be warming up to 40-65 ℃ and drip initiator after being uniformly dispersed, promptly finish through 4-8 hour polyreaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100386807A CN100395281C (en) | 2005-04-01 | 2005-04-01 | Aqucous polyurethane modified from vinyl resin possessing structure of bisphenol A and its preparing process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100386807A CN100395281C (en) | 2005-04-01 | 2005-04-01 | Aqucous polyurethane modified from vinyl resin possessing structure of bisphenol A and its preparing process |
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| Publication Number | Publication Date |
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| CN1687191A true CN1687191A (en) | 2005-10-26 |
| CN100395281C CN100395281C (en) | 2008-06-18 |
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| CNB2005100386807A Expired - Fee Related CN100395281C (en) | 2005-04-01 | 2005-04-01 | Aqucous polyurethane modified from vinyl resin possessing structure of bisphenol A and its preparing process |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898615A (en) * | 2012-09-11 | 2013-01-30 | 青岛文创科技有限公司 | Method for modification of waterborne polyurethane by using epoxy resin |
| CN106832185A (en) * | 2017-01-04 | 2017-06-13 | 上海华峰材料科技研究院（有限合伙） | Epoxy-capped polyurethane resin of use for synthetic leather large arch dam and preparation method thereof |
| CN108949075A (en) * | 2018-07-11 | 2018-12-07 | 翟琳 | A kind of preparation method of concrete crack repair sheets |
| CN111793351A (en) * | 2020-07-07 | 2020-10-20 | 中国人民解放军海军工程大学 | Polyurethane/vinyl resin IPN damping material and preparation method thereof |
| CN112940263A (en) * | 2021-02-26 | 2021-06-11 | 美高微球(南通)科技有限公司 | Vinyl resin, preparation method thereof and thickened vinyl resin composition |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR950006914B1 (en) * | 1991-12-11 | 1995-06-26 | 주식회사코오롱 | Adhesive composition for flexible pcb |
| JP2003122201A (en) * | 2001-10-17 | 2003-04-25 | Ricoh Co Ltd | Image forming apparatus |
-
2005
- 2005-04-01 CN CNB2005100386807A patent/CN100395281C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898615A (en) * | 2012-09-11 | 2013-01-30 | 青岛文创科技有限公司 | Method for modification of waterborne polyurethane by using epoxy resin |
| CN106832185A (en) * | 2017-01-04 | 2017-06-13 | 上海华峰材料科技研究院（有限合伙） | Epoxy-capped polyurethane resin of use for synthetic leather large arch dam and preparation method thereof |
| CN108949075A (en) * | 2018-07-11 | 2018-12-07 | 翟琳 | A kind of preparation method of concrete crack repair sheets |
| CN111793351A (en) * | 2020-07-07 | 2020-10-20 | 中国人民解放军海军工程大学 | Polyurethane/vinyl resin IPN damping material and preparation method thereof |
| CN111793351B (en) * | 2020-07-07 | 2022-08-12 | 中国人民解放军海军工程大学 | Polyurethane/vinyl resin IPN damping material and preparation method thereof |
| CN112940263A (en) * | 2021-02-26 | 2021-06-11 | 美高微球(南通)科技有限公司 | Vinyl resin, preparation method thereof and thickened vinyl resin composition |
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| CN100395281C (en) | 2008-06-18 |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Chizhou Jiuhua High-Go Electrical & Material Co., Ltd. Assignor: Hefei University of Technology Contract fulfillment period: 2009.7.10 to 2016.7.9 contract change Contract record no.: 2009340000129 Denomination of invention: Aqucous polyurethane modified from vinyl resin possessing structure of bisphenol A and its preparing process Granted publication date: 20080618 License type: Exclusive license Record date: 2009.7.20 |
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| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2009.7.10 TO 2016.7.9; CHANGE OF CONTRACT Name of requester: CHIZHOU JIUHUA HIGH-GO ELECTRICAL + MATERIAL CO., Effective date: 20090720 |
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| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080618 Termination date: 20110401 |