CN101613451A - High-content aqueous polyurethane latex and preparation method - Google Patents

High-content aqueous polyurethane latex and preparation method Download PDF

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Publication number
CN101613451A
CN101613451A CN200910012952A CN200910012952A CN101613451A CN 101613451 A CN101613451 A CN 101613451A CN 200910012952 A CN200910012952 A CN 200910012952A CN 200910012952 A CN200910012952 A CN 200910012952A CN 101613451 A CN101613451 A CN 101613451A
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Prior art keywords
reaction
chainextender
aqueous polyurethane
preparation
methyl
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CN200910012952A
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CN101613451B (en
Inventor
严欣宁
唐丽
杨文堂
荣星
樊丽君
刘杰
沈德全
赵瑞佳
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Tancheng Huachen Coatings Co ltd
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Liaoning Hengxing Fine Chemical (Group) Co Ltd
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Abstract

High-content aqueous polyurethane latex of the present invention and preparation method, adopt (A) hydrogenated diphenyl methane diisocyanate, (B) aliphatie diamine base sulfonate sodium, (C) Linear Double hydroxyalkyl siloxanes, (D) dimer acid polyester dibasic alcohol, (E) 2-methyl-2,4 pentanediols, (F) 1,3 cyclohexanediols, (G) chainextender, (H) fatty alcohol-polyoxyethylene ether TO7, (J) deionized water are made through prepolymerization reaction, chain extending reaction, emulsion reaction technology.Its production cost is low, and solid content is up to 55%, water-fast pressing, fastness, wear-resisting, washing fastness good, aqueous, environmental protective.

Description

High-content aqueous polyurethane latex and preparation method
Technical field
The present invention relates to a kind of used for textile coating layers aqueous polyurethane emulsion and preparation method, particularly relate to a kind of water pressure resistance good high-content aqueous polyurethane latex and preparation method.
Background technology
Along with the development of society, environmental protection more and more is subject to people's attention, and the aqueous product environmentally safe, human body is not had injury, so aqueous polyurethane replaces solvent borne polyurethane to become inexorable trend.
General aqueous polyurethane emulsion solid content is between 20-35% at present.The aqueous polyurethane emulsion solid content that can be used for fabric coating reaches that 40% product is also rare, and the WIT-769 of Britain Baxenden company, solid content are 40%, but and is not suitable for and improves the textiles water pressure resistance.Chinese patent CN1718606A discloses a kind of " aqueous polyurethane emulsion, its Manufacturing approach and use ", and its solid amount is about 30%, is used for water-borne coatings or water-based printing ink.
Summary of the invention
The purpose of this invention is to provide a kind of used for textile coating layers aqueous polyurethane emulsion and preparation method, particularly provide a kind of water pressure resistance good, fastness, wear-resisting, high-content aqueous polyurethane latex and preparation method that washing fastness is good.
Aqueous polyurethane emulsion of the present invention:
The raw material weight proportioning:
A, hydrogenated diphenyl methane diisocyanate (H 12MDI) 100-120
B, aliphatie diamine base sulfonate sodium (equivalent 220) 20-30
C, Linear Double hydroxyalkyl siloxanes (molecular weight 1000) 50-70
D, dimer acid polyester dibasic alcohol (molecular weight 2000) 40-70
E, 2-methyl-2,4 pentanediol 35-45
F, 1,3 cyclohexanediol 25-35
G, chainextender 6-10
H, fatty alcohol-polyoxyethylene ether TO7 5-10
J, deionized water 220-291
Make through prepolymerization reaction, chain extending reaction, emulsion reaction technology;
The product chemical index is as follows:
Outward appearance: white emulsion
Ionic: the moon
PH value: 8 ± 1
Solid content: 55 ± 1%
Chainextender (G) can be selected quadrol or 1, and 4-butyleneglycol one or the two are mixed use.
The above-mentioned aliphatie diamine base sulfonate sodium of mentioning (equivalent 220) can be selected the VESTAMIN A95 of degussa company.
Linear Double hydroxyalkyl siloxanes (molecular weight 1000) can be selected the Rhodrsil1647 of Rhodia.
Dimer acid polyester dibasic alcohol (molecular weight 2000) can be selected the long-chain dimer acid polyester dibasic alcohol PRIPLAST 3190 of UNIQEMA company.
Fatty alcohol-polyoxyethylene ether TO7 is an isomery C13 fatty alcohol-ether (7EO), is the product Lutensol TO7 of German BASF (BASF) company.
Aqueous polyurethane emulsion preparation method of the present invention:
Raw material weight proportioning: as previously mentioned;
The preparation method:
(1) prepolymerization reaction: (A) hydrogenated diphenyl methane diisocyanate, (C) Linear Double hydroxyalkyl siloxanes, (D) dimer acid polyester dibasic alcohol are added in the reactor, be warming up to 70-90 ℃ of reaction 2-4 hour, add (B) aliphatie diamine base sulfonate sodium, (E) 2-methyl-2 then, 4 pentanediols, the reaction of (F) 1,3 cyclohexanediol 2-5 hour;
(2) chain extending reaction: add (G) chainextender in the above-mentioned performed polymer,, be cooled to 40 ± 5 ℃ 50-80 ℃ of reaction 2-3 hour;
(3) emulsion reaction: add (H) fatty alcohol-polyoxyethylene ether TO7 and (J) deionized water, use high speed dispersor to disperse fast, product.
Aqueous polyurethane emulsion of the present invention is produced simple and convenient, and production cost is low, and solid content is up to 55%, water-fast pressing, fastness, wear-resisting, washing fastness good, aqueous, environmental protective.
The raw material hydrogenated diphenyl methane diisocyanate that the present invention selects has ring texture, ring texture is stable in the building-up process, still can exist after forming superpolymer, this structure can increase the rigidity of product, good springiness, can improve the fluffy sense of coating at water-fast, anti-solvent when wear resisting property is enhanced; The easy hydrolysis of ester bond in the conventional polyester produces chain rupture, the product instability, and the present invention selects for use the dimer acid polyester dibasic alcohol to have 36 carbon, and snappiness is splendid, has the dimeracid special construction simultaneously again, coating emulsion hydrolytic resistance obtains very big reinforcement, and stability of emulsion is improved; Linear Double hydroxyalkyl siloxanes provides soft and smooth segment, and siloxane structure has singularity, and it alternately is made of the polymer of stabilization of bony frame Siliciumatom and Sauerstoffatom.Its main chain-Si-O-Si-of polysiloxane belongs to inorganic structure, and its bond energy is higher than the bond energy of C-C key far away, and the bond energy of Si-C key is also than higher, and simple thermal motion is difficult to make Si-O key and Si-C key to rupture, thereby polysiloxane has good thermostability.The main chain of siloxanes is made up of siloxane bond in addition, and its bond length length, bond angle and bond energy are big, so siloxanes is very submissive, its viscous flow activation energy is very little, and when temperature was reduced to-136 ℃, also there was sub-chain motion in polydimethylsiloxane, and low temperature resistant, winter hardiness is special good.Secondly, do not have unsaturated link(age) on the siloxane main chain, and the Si-O-Si key is very stable to oxygen, ozone and ultraviolet ray etc., thereby has good weathering resistance.Siloxane structure determines it to have excellent hydrophobicity, he is close to the contact angle and the paraffin of water, thereby be widely used as water-proof material, reduce to handle the water-permeable and the water-absorbent of back fabric greatly, and do not destroy its ventilation property, mechanicalness and other performance, observe from molecular structure, hydroxyl links to each other with Siliciumatom on the main chain with the σ key in the Linear Double hydroxyalkyl siloxanes, increased the spatial volume that rotates freely, the hydrogen atom of hydroxyl and water hydrogen atom repel mutually, be that water molecules is difficult to combine with hydrophilic oxygen, thereby hydrophobic effect is provided.To sum up, siloxanes has improved flexibility, thermotolerance, winter hardiness, weathering resistance, hydrophobicity etc.; Adopt 2-methyl-2,4 pentanediol, 1,3 cyclohexanediol to carry out chain extension, owing to contain pendant methyl and ring texture has increased repulsion between products molecule, reduce emulsion viscosity, be able to high-load realization, further increased water-fast, anti-solvent, wear resisting property simultaneously; Select for use anionic hydrophilic group and nonionic emulsifying agent to work in coordination with effectiveness, stability of emulsion is further strengthened, and the coating penetration that the product of invention makes is better, with cloth cover to combine fastness good.Selected for use different types of hydroxyl raw material to improve performances such as product is wear-resisting, water-fast, washable, heat-resisting, cold-resistant during the present invention is synthetic.This product has good process implementing, and is environment friendly and pollution-free.Because the solids content height has not only reduced synthesis procedure, has reduced production cost, and the storing safe ready, transportation cost also reduced simultaneously.
Embodiment
Embodiment 1
The raw material weight proportioning:
(A) hydrogenated diphenyl methane diisocyanate 100, (B) aliphatie diamine base sulfonate sodium (equivalent 220) 20, (C) Linear Double hydroxyalkyl siloxanes (molecular weight 1000) 50, (D) dimer acid polyester dibasic alcohol (molecular weight 2000) 40, (E) 2-methyl-2,4 pentanediols 35, (F) 1,3 cyclohexanediol 25, (G) quadrol 7, (H) fatty alcohol-polyoxyethylene ether TO7 are 5, (J) deionized water: 220
The preparation method:
1, prepolymerization reaction: (A) hydrogenated diphenyl methane diisocyanate, (C) Linear Double hydroxyalkyl siloxanes (molecular weight 1000), (D) dimer acid polyester dibasic alcohol (molecular weight 2000) are added in the reactor, 75-80 ℃ of reaction 3 hours, add (B) aliphatie diamine base sulfonate sodium (equivalent 220), (E) 2-methyl-2 then, 4 pentanediols, (F) 1,3 cyclohexanediols continue reaction 2 hours at 75-80 ℃;
2, chain extending reaction: add (G) quadrol in the above-mentioned performed polymer,, be cooled to 40-42 ℃ 65-70 ℃ of reaction 3 hours;
3, emulsion reaction: add (H) fatty alcohol-polyoxyethylene ether TO7 and (J) deionized water, use high speed dispersor to disperse fast, product, its solid content 55.5%.
This embodiment selects for use quadrol to make chainextender and forms the urea key, and rigidity is strong, and wear resistance is excellent.
Embodiment 2
Raw material weight proportioning: (A) hydrogenated diphenyl methane diisocyanate 110, (B) aliphatie diamine base sulfonate sodium (equivalent 220) 25, (C) Linear Double hydroxyalkyl siloxanes (molecular weight 1000) 50, (D) dimer acid polyester dibasic alcohol (molecular weight 2000) 50, (E) 2-methyl-2,4 pentanediols 40, (F) 1,3 cyclohexanediols 30, (G) quadrol 2 and 1,4-butyleneglycol 5, (H) fatty alcohol-polyoxyethylene ether TO7 are 8, (J) deionized water 235: the preparation method is with embodiment 1, product content 55.3%.
This embodiment product is because in the proportioning raw materials (A) and (E) bigger, feel slightly firmly; Select quadrol and 1, the common chain extension of 4-butyleneglycol acts synergistically, and water pressure resistance, wear resistance are good.
Embodiment 3
Raw material weight proportioning: (A) hydrogenated diphenyl methane diisocyanate 115, (B) aliphatie diamine base sulfonate sodium (equivalent 220) 25, (C) Linear Double hydroxyalkyl siloxanes (molecular weight 2000) 70, (D) dimer acid polyester dibasic alcohol (molecular weight 2000) 50, (E) 2-methyl-2,4 pentanediols 40, (F) 1,3 cyclohexanediols 35, (G) 1,4-butyleneglycol 7, (H) fatty alcohol-polyoxyethylene ether TO7 are 8, (J) deionized water 261: the preparation method is with embodiment 1, product content 55.2%
This embodiment product is because in the material component proportioning (A) and (C) bigger, product water pressure resistance height, and feel is soft, and fastness is good.
Embodiment 4
Raw material weight proportioning: (A) hydrogenated diphenyl methane diisocyanate 115, (B) aliphatie diamine base sulfonate sodium (equivalent 220) 30, (C) Linear Double hydroxyalkyl siloxanes (molecular weight 1000) 60, (D) dimer acid polyester dibasic alcohol (molecular weight 2000) 60, (E) 2-methyl-2,4 pentanediols 35, (F) 1,3 cyclohexanediols 25, (G) 1,4-butyleneglycol 9, (H) fatty alcohol-polyoxyethylene ether TO7 are 10, (J) deionized water 255: the preparation method is with embodiment 1, product content 54.9%
This embodiment product is because (B) and (H) large usage quantity in the material component proportioning, and the product wetting ability is stronger, and emulsion state is good, good stability.
Embodiment 5
Raw material weight proportioning: (A) hydrogenated diphenyl methane diisocyanate 120, (B) aliphatie diamine base sulfonate sodium (equivalent 220) 30, (C) Linear Double hydroxyalkyl siloxanes (molecular weight 1000) 70, (D) dimer acid polyester dibasic alcohol (molecular weight 2000) 70, (E) 2-methyl-2,4 pentanediols 40, (F) 1,3 cyclohexanediols 30, (G) 1,4-butyleneglycol 9, (H) fatty alcohol-polyoxyethylene ether TO7 are 6, (J) deionized water 274: the preparation method is with embodiment 1, product content 55.4%
(C), (D) large percentage in this embodiment material component proportioning, its product pliability is good, and washing fastness is best.
Aqueous polyurethane emulsion fabric coating using method of the present invention: this emulsion is clung to the thickening agent PTF thickening with thickening material-vapour, and viscosity reaches 3000 ± 200 centipoises (25 ℃), uses coating machine coating on fabric then, dries 2 minutes for 150-165 ℃.
The present invention and home and abroad like product contrast and experiment are as follows:
Coating-forming agent Solid content (%) Wear resisting property (inferior) Water pressure resistance (mmH before the washing 2O) Wash ten times water pressure resistance (mmH 2O) The oven dry thickness of filming
Embodiment 1 ??55.5 ??≥5000 ??2380 ??2250 ??45
Embodiment 2 ??55.3 ??≥5000 ??2532 ??2450 ??43
Embodiment 3 ??55.2 ??≥5000 ??2510 ??2490 ??42
Embodiment 4 ??54.9 ??≥5000 ??2430 ??2390 ??41
Embodiment 5 ??55.4 ??≥5000 ??2360 ??2330 ??43
Wenzhou whole world URA301G ??35±1 ??2480 ??1840 ??1578 ??31
The WIT-769 of Britain Baxenden company ??40±1 ??3260 ??2230 ??1920 ??35
1, water pressure resistance detects: GB/T4744-1997 textile fabric water permeability resistance is measured hydrostatic test; ISO-811 water permeability resistance tester.
2, coat thickness detection: GB/1764-79 (89) paint film thickness test; JR-706 coat-thickness tester.
3, washing fastness detects: the test of GB/T8629-2001 textiles home washings and drying program; Cygnet XPB55-518S washing machine.
4, wear resistance detects: coated fabric wear resisting property measuring method; Fabric plain grinding instrument FZ/T01011-91.
From above test result as can be seen, product of the present invention is better than the high 20-30% of like product coating thickness, wear resistance, the water pressure resistance height, and fastness to washing is good, obviously is better than other products.
Annex:
1, the VESTAMIN A95 product description portion of degussa company, one page.
2, the Rhodrsil 1647 product description portions of Rhodia, two pages.
3, the long-chain dimer acid polyester dibasic alcohol PRIPLAST 3190 product description portions of UNIQEMA company, two pages.
4, the product Lutensol TO7 of German BASF (BASF) company product description portion, one page.

Claims (3)

1, high-content aqueous polyurethane latex is characterized in that:
The raw material weight proportioning:
A, hydrogenated diphenyl methane diisocyanate 100-120
B, aliphatie diamine base sulfonate sodium equivalent 220 20-30
C, Linear Double hydroxyalkyl siloxane molecule amount 1000 50-70
D, dimer acid polyester dibasic alcohol molecular weight 2000 40-70
E, 2-methyl-2,4 pentanediol 35-45
F, 1,3 cyclohexanediol 25-35
G, chainextender 6-10
H, fatty alcohol-polyoxyethylene ether T07 5-10
J, deionized water 220-291
Make through prepolymerization reaction, chain extending reaction, emulsion reaction technology;
The product chemical index is as follows:
Outward appearance: white emulsion
Ionic: the moon
PH value: 8 ± 1
Solid content: 55 ± 1%
Chainextender (G) can be selected quadrol or 1, and 4-butyleneglycol one or the two are mixed use.
2, high-content aqueous polyurethane latex preparation method is characterized in that:
The raw material weight proportioning:
A, hydrogenated diphenyl methane diisocyanate 100-120
B, aliphatie diamine base sulfonate sodium equivalent 220 20-30
C, Linear Double hydroxyalkyl siloxane molecule amount 1000 50-70
D, dimer acid polyester dibasic alcohol molecular weight 2000 40-70
E, 2-methyl-2,4 pentanediol 35-45
F, 1,3 cyclohexanediol 25-35
G, chainextender 6-10
H, fatty alcohol-polyoxyethylene ether T07 5-10
J, deionized water 220-291
The preparation method:
(1) prepolymerization reaction: (A) hydrogenated diphenyl methane diisocyanate, (C) Linear Double hydroxyalkyl siloxanes, (D) dimer acid polyester dibasic alcohol are added in the reactor, be warming up to 70-90 ℃ of reaction 2-4 hour, add (B) aliphatie diamine base sulfonate sodium, (E) 2-methyl-2 then, 4 pentanediols, the reaction of (F) 1,3 cyclohexanediol 2-5 hour;
(2) chain extending reaction: add (G) chainextender in the above-mentioned performed polymer,, be cooled to 40 ± 5 ℃ 50-80 ℃ of reaction 2-3 hour;
(3) emulsion reaction: add (H) fatty alcohol-polyoxyethylene ether T07 and (J) deionized water, use high speed dispersor to disperse fast, product.
3, high-content aqueous polyurethane latex preparation method according to claim 2, it is characterized in that: (G) chainextender can be selected quadrol or 1, and 4-butyleneglycol one or the two are mixed use.
CN2009100129524A 2009-08-05 2009-08-05 High-content aqueous polyurethane latex and preparation method thereof Expired - Fee Related CN101613451B (en)

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CN102505500A (en) * 2011-11-01 2012-06-20 吴江市北厍盛源纺织品助剂厂 Preparation method for novel radiation-proof coating agent
CN103484008A (en) * 2013-09-03 2014-01-01 盐城市昶桦户外用品有限公司 Organic silicon modified water-based polyurethane paint and preparation method
CN104975521A (en) * 2015-07-06 2015-10-14 辽宁恒星精细化工有限公司 Waterborne polyurethane latex emulsion for nylon fabric and preparation method thereof
CN105418883A (en) * 2015-12-08 2016-03-23 佛山佛塑科技集团股份有限公司 Waterborne polyurethane acrylate, waterborne ultraviolet-curable paint thereof and corresponding preparing method
CN107057032A (en) * 2017-04-26 2017-08-18 合肥科天水性科技有限责任公司 A kind of high-performance water-based polyurethane resin and preparation method for spinning coating
CN108359072A (en) * 2018-03-16 2018-08-03 上海汇得科技股份有限公司 A kind of high wet and heat ageing resistant polyester-type sofa artificial leather polyurethane tie layer resins and preparation method thereof
CN110684172A (en) * 2019-11-12 2020-01-14 东莞市米儿塑胶原料有限公司 Water-pressure-resistant water-based polyurethane resin
CN111875774A (en) * 2020-08-05 2020-11-03 辽宁恒星精细化工有限公司 Preparation method of aqueous flame-retardant water-pressure-resistant polyurethane emulsion for fabric
CN112480352A (en) * 2020-11-24 2021-03-12 桐乡市正嵘纺织助剂有限公司 Aqueous polyurethane textile coating agent
CN114316206A (en) * 2021-12-14 2022-04-12 福建汇得新材料有限公司 Wet-process polyurethane resin and preparation method and application thereof

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CN102505500A (en) * 2011-11-01 2012-06-20 吴江市北厍盛源纺织品助剂厂 Preparation method for novel radiation-proof coating agent
CN102505500B (en) * 2011-11-01 2013-11-20 吴江市北厍盛源纺织品助剂厂 Preparation method for novel radiation-proof coating agent
CN103484008A (en) * 2013-09-03 2014-01-01 盐城市昶桦户外用品有限公司 Organic silicon modified water-based polyurethane paint and preparation method
CN104975521A (en) * 2015-07-06 2015-10-14 辽宁恒星精细化工有限公司 Waterborne polyurethane latex emulsion for nylon fabric and preparation method thereof
CN104975521B (en) * 2015-07-06 2016-11-30 辽宁恒星精细化工有限公司 Nylon facing material aqueous polyurethane rubber cement emulsion and preparation method
CN105418883A (en) * 2015-12-08 2016-03-23 佛山佛塑科技集团股份有限公司 Waterborne polyurethane acrylate, waterborne ultraviolet-curable paint thereof and corresponding preparing method
CN107057032A (en) * 2017-04-26 2017-08-18 合肥科天水性科技有限责任公司 A kind of high-performance water-based polyurethane resin and preparation method for spinning coating
CN108359072A (en) * 2018-03-16 2018-08-03 上海汇得科技股份有限公司 A kind of high wet and heat ageing resistant polyester-type sofa artificial leather polyurethane tie layer resins and preparation method thereof
CN108359072B (en) * 2018-03-16 2020-12-08 上海汇得科技股份有限公司 Polyurethane adhesive layer resin for high-humidity-heat-aging-resistance polyester sofa leather and preparation method thereof
CN110684172A (en) * 2019-11-12 2020-01-14 东莞市米儿塑胶原料有限公司 Water-pressure-resistant water-based polyurethane resin
CN111875774A (en) * 2020-08-05 2020-11-03 辽宁恒星精细化工有限公司 Preparation method of aqueous flame-retardant water-pressure-resistant polyurethane emulsion for fabric
CN112480352A (en) * 2020-11-24 2021-03-12 桐乡市正嵘纺织助剂有限公司 Aqueous polyurethane textile coating agent
CN114316206A (en) * 2021-12-14 2022-04-12 福建汇得新材料有限公司 Wet-process polyurethane resin and preparation method and application thereof
CN114316206B (en) * 2021-12-14 2023-10-24 福建汇得新材料有限公司 Wet polyurethane resin and preparation method and application thereof

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