CN1772784A - Prepn and application of composite emulsion for base sloth coating of man made fur - Google Patents
Prepn and application of composite emulsion for base sloth coating of man made fur Download PDFInfo
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- CN1772784A CN1772784A CN 200510030373 CN200510030373A CN1772784A CN 1772784 A CN1772784 A CN 1772784A CN 200510030373 CN200510030373 CN 200510030373 CN 200510030373 A CN200510030373 A CN 200510030373A CN 1772784 A CN1772784 A CN 1772784A
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Abstract
The preparation process of composite emulsion for base cloth coating of man made fur includes the following steps: 1. vacuum dewatering polyether at 90-110 deg.c for 1-5 hr, preopolymerizing with diisocyanate in the molar NCO/OH ratio of 1.5-3 at 70-90 deg.c for 1-5 hr, lowering the temperature and adding viscosity reducer to lower viscosity; 2. adding chain expander for chain expanding reaction of 0.5-5 hr; 3. adding neutralizing agent to control pH 7; 4. lowering the temperature and adding no-ion water for self-emulsification; 5. adding initiator to initiate emulsion polymerization to obtain composite polyurethane/polyacrylate emulsion. The composite emulsion is used for coating knitted base cloth of man made fur. The present invention has the advantages of optimized preparation process, low cost, less environmental pollution, etc.
Description
Technical field
The present invention relates to a kind of preparation method and application thereof that is used for the coated on knitted cloth substrate of artificial fur emulsion, particularly relate to a kind of preparation method and application thereof of polyurethane/acrylic ester composite emulsion.
Background technology
Along with the application of fur imitation in dress ornament, garment industry constantly expanded, require fur imitation to have different styles and performance.Fur imitation is made up of artificial wool and base fabric, different Top Blending ratios, and different weaves and base sloth coating etc. all can influence the performance and the style thereof of fur imitation.For a long time, as the slurry of base sloth coating of man made fur, the most commonly used is polyacrylate dispersion.This class slurry has advantages such as cost dimensional stability low, that fabric is formalized is good.But the cementability and the perviousness to fabric of water polyacrylic acid slurry are relatively poor, after the coating depilation of fabric serious and feel is harder, therefore can only be applied to general woolen toy.For the fur imitation dress ornament clothes and the toy product of having relatively high expectations, such product performance do not reach necessary requirement.Urethane has good cementability and snappiness, especially still can show good elasticity and rebound resilience under low temperature environment.But domestic be used for fabric coating mostly be solvent borne polyurethane greatly, the production process environmental pollution is serious.
Along with the enhancing of people's environmental consciousness, the exploitation and the application of aqueous polyurethane coating have been subjected to extensive concern in recent years.This study group has successfully developed a kind of polyaminoester emulsion [seeing patent ZL02136588.1] that is used for coated on knitted cloth substrate of artificial fur, but find that in practice this kind product has improved the performance of the knitting artificial fur that is coated with really, as: dose,epilation reduces, drape is good, but also there is certain defective, drying rate is slower, and the fur base fabric has sticking sense after the coating.Simultaneously, in this Synthesis of Waterborne Polyurethane process, need to reduce the viscosity of polyurethane reaction system,, again the organic solvent decompression is extracted after the emulsification so that polymerization and later stage emulsifying power are carried out smoothly with acetone and other organic solvent.This process not only increases the cost of product, and the waste resource.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method and application thereof that is used for the polyurethane/acrylic ester composite emulsion of base sloth coating of man made fur, to remedy the deficiencies in the prior art and defective, meets the demands of production and living.
In order to solve the problems of the technologies described above, the technical solution adopted in the present invention is: a kind of preparation method who is used for the composite emulsion of foundation fabric of fur-type fabric, it is characterized in that, and comprise the steps:
(1) with polyethers at 90-110 ℃ of following vacuum hydro-extraction 1-5 hour, with stoichiometric vulcabond at 70-90 ℃ of pre-polymerization 1-5 hour, vulcabond (NCO) is 1.5～3: 1 with the mol ratio of hydroxyl (OH), is cooled to 40-50 ℃, adds the viscosity that viscosity-depression agent reduces prepolymer;
(2) adding chainextender carried out chain extending reaction 0.5-5 hour;
(3) add neutralizing agent and neutralize, the control pH value is 7;
(4) be cooled to 30-40 ℃, add deionized water and carry out self-emulsifying;
(5) add initiator, cause letex polymerization, obtain polyurethane/acrylic ester composite emulsion.
As optimized technical scheme: have following structure in the used chain extender component; The weight percentage that the consumption of chainextender accounts for total polymer weight is 1-15%.
R1, R2, R3 are that carbon atom is 1～3 alkyl
Used chainextender is carboxylic dibasic alcohol and common dibasic alcohol; Carboxylic dibasic alcohol is one or more in dimethylol propionic acid (DMPA), the dimethylolpropionic acid; Common dibasic alcohol is ethylene glycol, butyleneglycol, one or more in quadrol, diethyl triamine, tolylene diamine, the cyclohexanediamine.
Used vulcabond comprises aromatic diisocyanate and aliphatic diisocyanate, be tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), different Buddhist diketone vulcabond (IPDI), 1,6-hexamethylene-diisocyanate (HDI), dicyclohexyl methane diisocyanate (HMDI), Xylene Diisocyanate (XDI), one or more in the vulcabond (NDI) how.
Used polyethers is that molecular weight is the two functionality terminal hydroxy group polyethers of 400-4000, is in polyoxyethylene glycol, polytetrahydrofuran and the polypropylene glycol one or more.
Used viscosity-depression agent is an acrylic ester compound, is in methyl methacrylate, methyl acrylate, ethyl propenoate, the butyl acrylate one or more, and its add-on is 10～70% of a total polymer weight.
Used neutralizing agent is the tertiary amine compound of the two keys of band, is in dimethyl allylamine, methyl diallylamine, methacrylic acid-2-(dimethylamino) ethyl ester one or more.
Used initiator is one or more in Diisopropyl azodicarboxylate (AIBN), the Potassium Persulphate (KPS), and its consumption is 0.1～2% of a viscosity-depression agent.
Described composite emulsion can be used for coated on knitted cloth substrate of artificial fur.
The invention has the beneficial effects as follows: not only optimized preparation technology, reduced the cost of polyaminoester emulsion, reduced environmental pollution, economized on resources, it is slow also to have improved in the coatings applications existing oven dry simultaneously, and the fur base fabric has shortcomings such as sticking sense after the coating.
Embodiment
Below in conjunction with specific embodiment the present invention is further elaborated.Table 1 is the component and the proportioning of preparation composite emulsion
| Raw material | Parts by weight |
| PPG (molecular weight=2000) | 40 |
| Diphenylmethanediisocyanate (MDI) | 12 |
| Dimethylol propionic acid (DMPA) | 1.34 |
| 1, the 4-butyleneglycol | 0.9 |
| Dimethyl allylamine | 0.85 |
| Quadrol (TEA) | 0.048 |
| Methyl methacrylate (MMA) | 40 |
| Diisopropyl azodicarboxylate (AIBN) | 0.5 |
| Deionized water | 300 |
Embodiment 1
In being housed, the 1000ml there-necked flask of agitator, reflux exchanger, thermometer adds at 1 hour polypropylene glycol of 90 ℃ of vacuum hydro-extraction (PPG) and diphenylmethanediisocyanate (MDI).Slowly heating under constantly stirring, reaction mixture temperature rise to 80 ℃ and keep 3 hours after, be cooled to 50 ℃, add 10% the methyl methacrylate that accounts for total polymer weight and reduce viscosity; Add 1% the chainextender DMPA account for total polymer weight and the mixture of butyleneglycol, react after 5 hours; Add the neutralizing agent dimethyl allylamine and stir after 3 hours, the control pH value is 7, is cooled to 40 ℃ of adding deionized waters and carries out self-emulsifying, obtains the PU/MMA mixed emulsion; Add consumption then and be 0.1% initiator A IBN of viscosity-depression agent, stir, be warming up to 90 ℃, initiated polymerization 5 hours is measured according to GB, obtains solid content and be 24%, viscosity is the polyurethane/acrylic ester composite emulsion that 90 centipoises, particle diameter are about 120nm.
Embodiment 2
Preparation process is with embodiment 1, but the polyethers in the prescription change into equivalent polycaprolactone (PCL) (40g, M=2000).Measure according to GB, the gained solid content is 24%, viscosity is that 110 centipoises, particle diameter are the polyurethane/acrylic ester composite emulsion of 180nm.
Embodiment 3
Preparation process is with example 1, but the polyethers in the prescription change into equivalent PEG (40g, M=2000).Measure according to GB, the gained solid content is 24%, viscosity is that 70 centipoises, particle diameter are the polyurethane/acrylic ester composite emulsion of 100nm.
Embodiment 4
Preparation process is with example 1, but the methyl methacrylate (MMA) in the prescription such as changes at the MMA and the vinylbenzene St (MMA: St=9: 1) mixed solution of weight.Measure according to GB, the gained solid content is 24%, viscosity is that 95 centipoises, particle diameter are the polyurethane/acrylic ester composite emulsion of 150nm.
Embodiment 5
Preparation process is with example 1, but in the prescription isocyanic ester change into equivalent tolylene diisocyanate TDI-80 (8.38g, M=174.5).Measure according to GB, the gained solid content is 24%, viscosity is that 75 centipoises, particle diameter are the polyurethane/acrylic ester composite emulsion of 148nm.
Embodiment 6
Preparation process is with example 1, but the Diisopropyl azodicarboxylate (AIBN) in the prescription such as changes at the Potassium Persulphate (KPS) of weight.Measure according to GB, the gained solid content is 24%, viscosity is that 70 centipoises, particle diameter are the polyurethane/acrylic ester composite emulsion of 177nm.
Embodiment 7
Preparation process is with example 1, but the ABIN in the prescription such as changes at the KPS and the AIBN (KPS: AIBN=3: 1 mixture of weight.Measure according to GB, the gained solid content is 24%, viscosity is that 70 centipoises, particle diameter are the polyurethane/acrylic ester composite emulsion of 165nm.
Embodiment 8
Carry out base sloth coating with prepared polyurethane/acrylate emulsion, bake out temperature is 130 ℃, and drying time is 8 minutes.The plucking rate of the fur imitation that makes (according to FZ/T 72002-1993 standard testing) is 2.0 milligrams/100 square centimeters, and base fabric does not have sticking sense.
Comparative example 1
Grey cloth is fully identical with example 8 with complete processing, adopts the polyaminoester emulsion of preparation in the patent [ZL02136588.1] to carry out coating, and bake out temperature is 130 ℃, and drying time is 12 minutes.(according to the FZ/T72002-1993 standard testing), the plucking rate of the fur imitation of gained are 2.2 milligrams/100 square centimeters, and there is sticking sense in base fabric.
Claims (9)
1. a preparation method who is used for the composite emulsion of base sloth coating of man made fur is characterized in that, comprises the steps:
(1) with polyethers at 90-110 ℃ of following vacuum hydro-extraction 1-5 hour, with stoichiometric vulcabond at 70-90 ℃ of pre-polymerization 1-5 hour, the mol ratio of vulcabond and hydroxyl is 1.5～3: 1, is cooled to 40-50 ℃, adds the viscosity that viscosity-depression agent reduces prepolymer;
(2) adding chainextender carried out chain extending reaction 0.5-5 hour;
(3) add neutralizing agent and neutralize, the control pH value is 6.5-7.5;
(4) be cooled to 30-40 ℃, add deionized water and carry out self-emulsifying;
(5) add initiator, cause letex polymerization, obtain polyurethane/acrylic ester composite emulsion.
2. preparation method according to claim 1 is characterized in that: have following structure in the used chain extender component; The weight percentage that the consumption of chainextender accounts for total polymer weight is 1-15%,
R1, R2, R3 are that carbon atom is 1～3 alkyl.
3. preparation method according to claim 1 and 2 is characterized in that: used chainextender is carboxylic dibasic alcohol and common dibasic alcohol; Carboxylic dibasic alcohol is one or more in dimethylol propionic acid, the dimethylolpropionic acid; Common dibasic alcohol is ethylene glycol, butyleneglycol, one or more in quadrol, diethyl triamine, tolylene diamine, the cyclohexanediamine.
4. preparation method according to claim 1, it is characterized in that: used vulcabond comprises aromatic diisocyanate and aliphatic diisocyanate, be tolylene diisocyanate, diphenylmethanediisocyanate, different Buddhist diketone vulcabond, 1,6-hexamethylene-diisocyanate, dicyclohexyl methane diisocyanate, Xylene Diisocyanate, one or more in the vulcabond how.
5. preparation method according to claim 1 is characterized in that: used polyethers is that molecular weight is the two functionality terminal hydroxy group polyethers of 400-4000, is in polyoxyethylene glycol, polytetrahydrofuran and the polypropylene glycol one or more.
6. preparation method according to claim 1, it is characterized in that: used viscosity-depression agent is an acrylic ester compound, be in methyl methacrylate, methyl acrylate, ethyl propenoate, the butyl acrylate one or more, its add-on is 10～70% of a total polymer weight.
7. preparation method according to claim 1 is characterized in that: used neutralizing agent is the tertiary amine compound of the two keys of band, is in dimethyl allylamine, methyl diallylamine, the methacrylic acid-2-ethyl ester one or more.
8. preparation method according to claim 1 is characterized in that: used initiator is one or more in Diisopropyl azodicarboxylate, the Potassium Persulphate, and its consumption is 0.1～2% of a viscosity-depression agent.
9. the application as any described composite emulsion in the claim 1,2,4,5,6,7,8 is characterized in that: can be used for coated on knitted cloth substrate of artificial fur.
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| CNB2005100303734A CN100358930C (en) | 2005-10-11 | 2005-10-11 | Prepn and application of composite emulsion for base sloth coating of man made fur |
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| CNB2005100303734A CN100358930C (en) | 2005-10-11 | 2005-10-11 | Prepn and application of composite emulsion for base sloth coating of man made fur |
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| CN1772784A true CN1772784A (en) | 2006-05-17 |
| CN100358930C CN100358930C (en) | 2008-01-02 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102505485A (en) * | 2011-10-20 | 2012-06-20 | 天津工业大学 | Hair slip prevention finishing agent and finishing method for rabbit hair fabric |
| CN102558836A (en) * | 2011-12-30 | 2012-07-11 | 西南交通大学 | Spoke noise reduction damping polymer material and preparation method thereof |
| CN102977282A (en) * | 2012-12-06 | 2013-03-20 | 陕西科技大学 | Preparation method of anionic organic-solvent-free and emulsifier-free polyurethane microemulsion |
| CN105121507A (en) * | 2013-04-17 | 2015-12-02 | 赢创德固赛有限公司 | Alkoxysilyl-containing adhesive sealants with intrinsically reduced viscosity |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100497429C (en) * | 2002-01-18 | 2009-06-10 | 段友芦 | Aqueous polyurethane dispersing liquid and preparation thereof as tackiness agent and coating |
| US7001952B2 (en) * | 2002-04-19 | 2006-02-21 | Ppg Industries Ohio, Inc. | Coating compositions containing polyurethane dispersions and highly crosslinked polymer particles |
| CN1167724C (en) * | 2002-08-20 | 2004-09-22 | 东华大学 | Process for preparing polyurethane emulsion coated on knitted cloth substrate of artificial fur |
| CN1218981C (en) * | 2003-03-06 | 2005-09-14 | 华南理工大学 | Acrylic polyurethane copolymer emulsion, its preparation method and use |
| CN1318467C (en) * | 2004-08-04 | 2007-05-30 | 中国林业科学研究院林产化学工业研究所 | Fine emulsion polymerization method of polyurethane acrylic ester compound emulsion |
-
2005
- 2005-10-11 CN CNB2005100303734A patent/CN100358930C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102505485A (en) * | 2011-10-20 | 2012-06-20 | 天津工业大学 | Hair slip prevention finishing agent and finishing method for rabbit hair fabric |
| CN102558836A (en) * | 2011-12-30 | 2012-07-11 | 西南交通大学 | Spoke noise reduction damping polymer material and preparation method thereof |
| CN102977282A (en) * | 2012-12-06 | 2013-03-20 | 陕西科技大学 | Preparation method of anionic organic-solvent-free and emulsifier-free polyurethane microemulsion |
| CN105121507A (en) * | 2013-04-17 | 2015-12-02 | 赢创德固赛有限公司 | Alkoxysilyl-containing adhesive sealants with intrinsically reduced viscosity |
| CN105121507B (en) * | 2013-04-17 | 2017-08-15 | 赢创德固赛有限公司 | The adhesive/sealant containing alkoxysilyl with the viscosity inherently reduced |
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| CN100358930C (en) | 2008-01-02 |
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