CN102850516B - Aliphatic polyurethane resin preparation method - Google Patents
Aliphatic polyurethane resin preparation method Download PDFInfo
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Abstract
The invention relates to the technical field of materials for synthetic leather, in particular to an aliphatic polyurethane resin preparation method. The method includes the steps: 1) increasing the temperature of 35 parts of poly adipic acid glycol-butanediol ether glycol and 35 parts of polycaprolactone glycol to 100 DEG C, performing vacuum dehydration for about 1h and cooling to 50 DEG C, wherein the molecular weight of the poly adipic acid glycol-butanediol ether glycol is 3000, and the molecular weight of the polycaprolactone glycol is 1000; 2) adding 150 parts of methylbenzene, 83 parts of IPDI (isophorone diisocyanate), 19 parts of H12MDI (dicyclohexylmethane 4,4- diisocyanate) and 0.2 part of stannous octoate into a reactor with stirring uniformly, increasing the temperature to 90 DEG C and reacting for 3h; 3) adding 5 parts of 1,4-butanediol and 9 parts of neopentyl glycol to continue reaction for 3h at the temperature of 90 DEG C; 4) cooling to 50 DEG C, adding 250 parts of methylbenzene, 200 parts of isobutyl alcohol and 200 parts of ethyl acetate with stirring uniformly, slowly tackifying with 13.8 parts of IPDA (isophorone diamine), and stopping adding the isophorone diamine when the viscosity is increased to 3000cps; and 5) continuing to stir for 30 minutes and cooling to 30 DEG C to discharge, so that weak-solvent aliphatic polyurethane resin with 20% of solid content and 180kgf/cm<2> of modulus is obtained.
Description
The present patent application is that number of patent application is: 2010101524769, and patent name is: Weak solvent aliphatic polyurethane resin for synthetic leather and preparation method thereof, the applying date is: the divisional application of the application for a patent for invention of 2010-4-21.
Technical field
The present invention relates to use for synthetic leather material technology field, particularly a kind of preparation method of aliphatic polyurethane resin.
Technical background
Aspect use for synthetic leather urethane resin, main use is aromatic product now, and its product price is relatively low, and synthesis technique is also relatively simple.But in aromatic series product, generally contain the strong solvents such as DMF, MEK, in the time of synthetic leather production and surface treatment, can produce corrosion to bottom bass, affect feel and the effect of synthetic leather.In addition, in aromatic urethane resin, owing to containing phenyl ring, be subject to uviolizing meeting open loop to cause resin xanthochromia, in light synthetic leather product, can cause product variable color when using.And aliphatic polyurethane resin is not containing phenyl ring, under ultraviolet irradiation, can keep for a long time stable.Along with quality, the kind of people to synthetic leather requires more and more higher, to there being the demand of Weak solvent aliphatic resin of environment-friendly type of superior ultraviolet light performance also increasing, on market, be mainly take imported product as main now, domestic in this respect also in the starting stage.
Before the present invention, the related invention patent of use for synthetic leather urethane resin mainly contains:
CN1781962 discloses a kind of production method of use for synthetic leather urethane resin, and it has adopted aromatic isocyanic ester, and in solvent, has used the intensive polar solvents such as DMF.Use the not resistance to xanthochromia of urethane resin that obtains of the method, and use bottom bass is had to corrosion, can only meet the needs of general synthetic leather product.
CN101092538 discloses a kind of aliphatics Waterproof Breathable synthetic leather and has covered with paint, lacquer, colour wash, etc. resin and pre-polymerization manufacture method thereof.In the method, use severe corrosive solvent butanone, and whole lower Weak solvents of corrodibility that adopt in the present invention, this patent has only been used polyether glycol as starting material simultaneously, although polyether glycol has good hydrolysis characteristic but its mechanical property and temperature tolerance are poor, application scenario is limited, the present invention can adopt polyester polyol, polyether glycol and both mixtures, not only can there is the product of good hydrolytic resistance, also can utilize the characteristic of polyester polyol to synthesize mechanical property good, the good product of the wear-resisting resistance to complications of temperature tolerance, the range of application of the product of expansion greatly.Although CN101092538 adopts aliphatic isocyanates, is only applied to synthetic leather surface daub on a wall.The aliphatic polyurethane resin of mentioning in the present invention not only can be applied to synthetic leather surface daub on a wall, also can be for the synthesis of leather dry production, application wider.
On synthesis technique, CN101092538 has only adopted amine chain extender in addition, but in actual production, amine chain extender and isocyanate reaction speed are very fast, carry out chain extension by amine chain extender merely, reaction is difficult to control, the quality of final product is difficult to guarantee, amine chain extender and isocyanic ester are produced urea groups simultaneously, urea groups is the carbamate not as hydroxyl in polyvalent alcohol and isocyanate reaction generation in flexibility, if all use amine chain extension, the urea groups generating too much will certainly affect the performance of product, the present invention adopts polyamine and polyvalent alcohol jointly as chainextender, not only reflection is steadily easily controlled, and polyvalent alcohol can by select different carbochain length and obtain different product performance.
CN101475742 discloses a kind of aromatic yellow-stain resistant polyurethane resin for synthetic leather and preparation method thereof.It adopts aromatic isocyanate, has used oxidation inhibitor to reach the object of xanthochromia, and resistance to xanthochromia effect is general, can only reach 4 grades.The present invention adopts group aliphatic resin, itself just has natural resistance to xanthochromia characteristic, and without adding oxidation inhibitor, resistance to xanthochromia reaches 5 grades, in performance considerably beyond the product of foregoing invention.
Summary of the invention
The object of the invention is to the deficiency for use for synthetic leather aromatic series product, first object of the present invention is to provide a kind of Weak solvent aliphatic polyurethane resin for synthetic leather, adopt technical scheme of the present invention, can synthesize the urethane resin of different solid contents, different viscosity, different modulus, meet the needs that synthetic leather is produced, prepare there is high thermal resistance, winter hardiness, non-stick property and the better synthetic leather product of color developing.Second object of the present invention is to provide above-mentioned Weak solvent aliphatic polyurethane resin for synthetic leather preparation method.
In order to realize first above-mentioned object, the present invention has adopted following technical scheme:
Use for synthetic leather weak solvent aliphatic polyurethane resin, this urethane resin is prepared by following component by weight percentage:
| Aliphatic diisocyanate compound | 2%～30% |
| Polyester or polyether alkylol cpd | 5%～40% |
| Small molecules polyvalent alcohol chainextender | 0%～10% |
| Small molecules polyamine chain extension | 0.1%～13% |
| Catalyzer | 0.1‰～1.0% |
| Auxiliary agent | 0.5‰～5.0% |
| Organic Weak solvent | 45%～85%； |
Polyester or polyether polyols molecular weight between 400～12000g/mol; In the amount of the hydroxylated material in polyester or polyether alkylol cpd component and small molecules polyvalent alcohol chain extender component and aliphatic diisocyanate compound component, the ratio of the amount of substance of vulcabond ester is 1:1.05 ~ 1:3.5; The amount of the hydroxylated material in polyester or polyether alkylol cpd component and small molecules polyvalent alcohol chain extender component adds that the ratio of the amount of substance of vulcabond in the amount of substance of amido in small molecules polyamine chainextender and aliphatic diisocyanate compound component is 0.7:1.3 ~ 1:1.
As preferably, above-mentioned urethane resin is prepared by following component by weight percentage:
| aliphatic diisocyanate compound | 8%～15% |
| polyester or polyether alkylol cpd | 5%～20% |
| small molecules polyvalent alcohol chainextender | 0.5%～5.0% |
| small molecules polyamine chain extension | 1.0%～6.0% |
| catalyzer | 0.1 ‰～1.0% |
| auxiliary agent | 0.5 ‰～5.0% |
| organic Weak solvent | 50%～80%. |
As preferably, described aliphatic diisocyanate compound is selected from one or more mixing in sym.-diisopropylideneacetone vulcabond, hexamethylene diisocyanate, two cyclohexyl methane diisocyanates.
As preferably, described polyester or polyether polyols are one or more mixing in polyoxypropyleneglycol, polytetrahydrofuran diol, polycaprolactone glycol, polycarbonate diol, polyethylene glycol adipate glycol, polydiethylene glycol adipate glycol, polybutylene glyool adipate, polypropylene adipate (PPA) glycol, polyhexamethylene adipate glycol, polyneopentyl glycol adipate glycol, poly-adipate glycol-Diethylene Glycol esterdiol, poly-adipate glycol-butanediol ester glycol.
As preferably, described small molecules polyvalent alcohol chainextender is ethylene glycol, Diethylene Glycol, 1,2-PD, BDO, 1,6 hexylene glycol, one or more mixing in neopentyl glycol, trimethylolpropane tris alcohol.
As preferably, described small molecules polyamine chainextender is different Buddhist diketone diamines and quadrol, and their mixture.
As preferably, described catalyzer is that organic tin comprises stannous octoate, dibutyl tin laurate and organo-bismuth class catalyzer or its mixture.
As preferably, described auxiliary agent is silicone based hand feeling agent, release agent, flow agent.
As preferably, described organic Weak solvent is that benzene class is as toluene, dimethylbenzene etc., ester class is as ethyl acetate, butylacetate etc., and ethers is as ethylene glycol monomethyl ether, propylene glycol monomethyl ether etc., and alcohols is as methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol and composition thereof.
In order to realize second above-mentioned object, the present invention has adopted following technical scheme:
Prepare an above-mentioned use for synthetic leather weak solvent aliphatic polyurethane resin, the method comprises the following steps:
(a) polyester or polyether polyols carry out the dry 0.5～2h of vaccum dewatering at 100 ℃;
(b) in reactor, add vulcabond, auxiliary agent, catalyzer, partial solvent and early stage to react needed part small molecules polyvalent alcohol chainextender, fully stir, at 60 ~ 90 ℃, react 2 ~ 4h;
(c) add the required small molecules polyvalent alcohol chainextender of second step, at 60 ~ 90 ℃, continue reaction 2 ~ 4h;
(d) cool to 20 ~ 50 ℃, add remaining solvent, stir;
(e) slowly add the chainextender chain extension of small molecules binary amine, in the time that system viscosity arrives 300cps ~ 300000cps viscosity, stop chain extension;
(f) cooling after reaction, metering, packing.
The present invention adopts the aliphatic diisocyanate that does not contain phenyl ring as raw material, synthetic product can xanthochromia under uviolizing, the progression of resistance to xanthochromia reaches 5 grades (according to the B method test stipulating in standard HG/T 3689-2001, test duration is 3 hours), and the resistance to xanthochromia of common aromatic urethane resin only has 2 ~ 3 grades.Adopted alcohol simultaneously, the solvent of ethers has substituted deep-etching, the N that toxicity is larger, dinethylformamide, butanone equal solvent, it is very little to the corrodibility of bass in the time that synthetic leather is produced, can keep feel and the characteristic of bass, in actual production, by product of the present invention with contain N, dinethylformamide, the urethane resin of butanone is coated the surface of synthetic leather wet method bass, can significantly observe, contain N, dinethylformamide, the urethane resin of butanone has strong corrosion to cause bass variable color to bass, and the synthetic leather wet method bass surface of coating product of the present invention does not significantly change.
In the present invention, by selecting different types of polyester and polyether glycol, can obtain the polyurethane products of different performance, meet the requirement to performance of various synthetic leather.In the time selecting polyether glycol and polytetrahydrofuran polyvalent alcohol, the aliphatic polyurethane resin obtaining has good hydrolytic resistance and winter hardiness, and product has better mechanical property and temperature tolerance while selecting polyester polyol, while selecting polycaprolactone glycol and polycarbonate diol, have two above features concurrently, but cost can be higher.
Aliphatic polyurethane resin is not owing to containing the rigid structures such as aromatic ring in the aliphatic isocyanates structure adopting, resin property is conventionally poor conventionally, is difficult to meet application demand.In order to solve the problem of poor performance, the present invention adopts alcohols and two kinds of chainextenders of amine to adjust its molecule segment structure, have the snappiness of alcohols chainextender and the rigidity of amine chain extender concurrently, and by optimizing synthesis technique, obtained a kind of weak solvent aliphatic polyurethane resin of better performances.According to the preparation method of Weak solvent aliphatic polyurethane resin for synthetic leather of the present invention, can synthesize the urethane resin of different solid contents, different viscosity, different modulus, meet the needs that synthetic leather is produced, prepare there is high thermal resistance, winter hardiness, non-stick property and the better synthetic leather product of color developing.
Embodiment
embodiment 1
By 53 parts of polybutylene glyool adipates (molecular weight 2000), 100 parts of polycarbonate diols (molecular weight 2000) are warmed up to 100 ℃, and the about 1h of vacuum hydro-extraction cools to 50 ℃; In reactor, add 150 parts of toluene, 61 parts of IPDI, 51 parts of HDI, 10 parts of ethylene glycol, 1 part of dibutyl tin laurate, stir, be warmed up to 80 ℃, reaction 3h; Add the BDO of 12 parts, 80 ℃ are continued reaction 3h; Cool to 50 ℃, after adding 150 parts of 200 parts of toluene, 200 parts of Virahols, ethyl acetate to stir, slowly use the different Buddhist diketone diamines tackify of 12 parts, in the time that viscosity is raised to 80000cps, stop adding different Buddhist diketone diamines; Continue to stir 30 minutes, be then cooled to 30 ℃, discharging; Obtaining solid content is 30%, and modulus is about 100kgf/cm
2weak solvent aliphatic polyurethane resin.
embodiment 2
162.7 parts of polytetrahydrofuran diols (molecular weight 2000) are warmed up to 100 ℃, and the about 1h of vacuum hydro-extraction, cools to 50 ℃; In reactor, add 150 parts of toluene, 32 parts of IPDI, 2 parts of organic hydroxy silicate auxiliary agents, 0.3 part of dibutyl tin laurate, stir, be warmed up to 90 ℃, reaction 2h; Add the BDO of 1 part, the Diethylene Glycol of 0.5 part continues anti-reaction 2h at 90 ℃; Cool to 50 ℃, add 50 parts of toluene, 300 parts of Virahols, 300 parts of propylene glycol monomethyl ethers, after stirring, slowly use the quadrol tackify of 1.5 parts, in the time that viscosity is raised to 5000cps, stops adding quadrol; Continue to stir 30 minutes, be then cooled to 30 ℃, discharging; Obtaining solid content is 20%, and modulus is 25kgf/cm
2weak solvent aliphatic polyurethane resin.
embodiment 3
The polycaprolactone glycol (molecular weight 1000) of 35 parts of poly-adipate glycol-butanediol ester glycol (molecular weight 3000) and 35 parts is warmed up to 100 ℃, and the about 1h of vacuum hydro-extraction, cools to 50 ℃; In reactor, add 150 parts of toluene, 83 parts of IPDI, 19 parts of H12MDI, 0.2 part of stannous octoate, stir, be warmed up to 90 ℃, reaction 3h; Add the BDO of 5 parts, the neopentyl glycol of 9 parts continues anti-reaction 3h at 90 ℃; Cool to 50 ℃, add 250 parts of toluene, 200 parts of isopropylcarbinols, 200 parts of ethyl acetate, after stirring, slowly use the IPDA tackify of 13.8 parts, in the time that viscosity is raised to 3000cps, stops adding different Buddhist diketone diamines; Continue to stir 30 minutes, be then cooled to 30 ℃, discharging; Obtaining solid content is 20%, and modulus is 180kgf/cm
2weak solvent aliphatic polyurethane resin.
embodiment 4
145 parts of polyneopentyl glycol adipate glycol (molecular weight 2000) are warmed up to 100 ℃, and the about 1h of vacuum hydro-extraction, cools to 50 ℃; In reactor, add 150 parts of toluene, 251 parts of IPDI, 5 parts of organic bismuth catalysts, stir, be warmed up to 90 ℃, reaction 2h; Add 1,6 hexylene glycol of 46 parts to continue anti-reaction 2h at 90 ℃; Cool to 50 ℃, add 100 parts of toluene, 100 parts of propyl carbinols, 100 parts of Virahols, after stirring, slowly use the different Buddhist diketone diamines tackify of 53 parts, in the time that viscosity is raised to 150000cps, stops adding different Buddhist diketone diamines; Continue to stir 30 minutes, be then cooled to 30 ℃, discharging; Obtaining solid content is 50%, and modulus is 220kgf/cm
2weak solvent aliphatic polyurethane resin.
embodiment 5
Say in order to verify Weak solvent aliphatic polyurethane resin of the present invention the resistance to xanthochromia characteristic having, resin prepared above-mentioned case is made to the film that thickness is about 0.2mm, test its anti-yellowing property according to the B method stipulating in standard HG/T 3689-2001, the test duration is 3 hours.After testing, the resin anti-yellowing property that prepared by described case has all reached 5 grade standards.
Claims (1)
1. a preparation method for aliphatic polyurethane resin, is characterized in that the method comprises the following steps:
1) by 35 parts of poly-adipate glycol-butanediol ester glycol, and the polycaprolactone glycol of 35 parts is warmed up to 100 ℃, poly-adipate glycol-butanediol ester glycol molecular weight 3000, and polycaprolactone glycol molecular weight 1000, vacuum hydro-extraction 1h, cools to 50 ℃;
2) in reactor, add 150 parts of toluene, 83 parts of IPDI, 19 parts of H12MDI, 0.2 part of stannous octoate, stir, be warmed up to 90 ℃, reaction 3h;
3) add the BDO of 5 parts, the neopentyl glycol of 9 parts continues reaction 3h at 90 ℃;
4) cool to 50 ℃, add 250 parts of toluene, 200 parts of isopropylcarbinols, 200 parts of ethyl acetate, after stirring, slowly use the IPDA tackify of 13.8 parts, in the time that viscosity is raised to 3000cps, stops adding isophorone diamine;
5) continue to stir 30 minutes, be then cooled to 30 ℃, discharging, obtaining solid content is 20%, modulus is 180kgf/cm
2weak solvent aliphatic polyurethane resin.
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| CN106554747B (en) * | 2016-10-17 | 2018-01-02 | 淄博奥德美高分子材料有限公司 | A kind of preparation method of high anti-fall smooth aqueous polyurethane transfer adhesive |
| CN106521957A (en) * | 2016-10-27 | 2017-03-22 | 江苏宝泽高分子材料股份有限公司 | Skin feeling scraper material treating agent for synthetic leather and preparation method of skin feeling scraper material treating agent |
| CN113583210A (en) * | 2021-08-12 | 2021-11-02 | 清远市番亿聚氨酯有限公司 | Yellowing-resistant polyurethane resin and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348554A (en) * | 2008-08-08 | 2009-01-21 | 山东东大一诺威聚氨酯有限公司 | Organosilicon modified aqueous polyurethane resin and preparation thereof |
| CN101381447A (en) * | 2008-10-14 | 2009-03-11 | 太仓市旭川树脂有限公司 | Polyurethane resin |
| CN101824132A (en) * | 2010-04-21 | 2010-09-08 | 浙江深蓝轻纺科技有限公司 | Weak solvent aliphatic polyurethane resin for synthetic leather and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348554A (en) * | 2008-08-08 | 2009-01-21 | 山东东大一诺威聚氨酯有限公司 | Organosilicon modified aqueous polyurethane resin and preparation thereof |
| CN101381447A (en) * | 2008-10-14 | 2009-03-11 | 太仓市旭川树脂有限公司 | Polyurethane resin |
| CN101824132A (en) * | 2010-04-21 | 2010-09-08 | 浙江深蓝轻纺科技有限公司 | Weak solvent aliphatic polyurethane resin for synthetic leather and preparation method thereof |
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Address after: 310000, 2, Jiang Shan Road, Mei Town, Jiande City, Zhejiang, Hangzhou Patentee after: Zhejiang deep blue new material Polytron Technologies Inc Address before: 313217 Zhejiang city of Huzhou province Deqing County Xin'an Xin Hui Road No. 120 Patentee before: Zhejiang Sunlight Textile Technology Co., Ltd. |