CN102850514A - Polyurethane resin preparation method - Google Patents
Polyurethane resin preparation method Download PDFInfo
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- CN102850514A CN102850514A CN2012103435010A CN201210343501A CN102850514A CN 102850514 A CN102850514 A CN 102850514A CN 2012103435010 A CN2012103435010 A CN 2012103435010A CN 201210343501 A CN201210343501 A CN 201210343501A CN 102850514 A CN102850514 A CN 102850514A
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Abstract
The invention relates to the technical field of materials for synthetic leather, in particular to a polyurethane resin preparation method. The method includes the steps: 1) increasing the temperature of 145 parts of polyneopentanediol adipate with the molecular weight of 2000 to 100 DEG C, performing vacuum dehydration for about 1h and cooling to 50 DEG C; 2) adding 150 parts of methylbenzene, 251 parts of IPDI (isophorone diisocyanate) and 5 parts of organic bismuth catalysts into a reactor with stirring uniformly, increasing the temperature to 90 DEG C and reacting for 2h; 3) adding 46 parts of 1,6-hexanediol to continue reaction for 2h at the temperature of 90 DEG C; 4) cooling to 50 DEG C, adding 100 parts of methylbenzene, 100 parts of normal butanol and 100 parts of isopropyl alcohol with stirring uniformly, slowly tackifying with 53 parts of isophorone diamine, and stopping adding the isophorone diamine when the viscosity is increased to 150000cps; and 5) continuing to stir for 30 minutes and cooling to 30 DEG C to discharge so that weak-solvent aliphatic polyurethane resin with 50% of solid content and 220kgf/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 dividing an 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 urethane resin.
Technical background
Aspect the 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 generally contain the strong solvents such as DMF, MEK in the aromatic series product, when synthetic leather production and surface treatment, can produce corrosion to the bottom bass, affect feel and the effect of synthetic leather.In addition, owing to contain phenyl ring, be subjected to uviolizing meeting open loop to cause the resin xanthochromia in the aromatic urethane resin, in the synthetic leather product that uses at light color, can cause the product variable color.And aliphatic polyurethane resin does not contain phenyl ring, can keep for a long time stable under ultraviolet irradiation.Along with people are more and more higher to quality, the kind requirement of synthetic leather, demand to the Weak solvent aliphatic resin of environment-friendly type that superior ultraviolet light performance is arranged is also increasing, mainly be take imported product as main on the market now, domesticly also be in this respect the starting stage.
The related invention patent of use for synthetic leather urethane resin mainly contains before the present invention:
CN1781962 discloses a kind of production method of use for synthetic leather urethane resin, and it has adopted aromatic isocyanic ester, and has used the intensive polar solvents such as DMF in the solvent.The not anti-xanthochromia of urethane resin that uses the method to obtain, and use the bottom bass is had corrosion, can only satisfy 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.Used severe corrosive solvent butanone in the method, and whole lower Weak solvents of corrodibility that adopt among the present invention, this patent has only been used polyether glycol as starting material simultaneously, although polyether glycol has preferably the hydrolysis characteristic but its mechanical property and temperature tolerance are relatively poor, the application scenario is limited, the present invention can adopt polyester polyol, polyether glycol and both mixtures, the product that not only can have good hydrolytic resistance, it is good also can to utilize the characteristic of polyester polyol to synthesize mechanical property, the good product of the wear-resisting anti-complications of temperature tolerance, the greatly range of application of the product of expansion.Although CN101092538 adopts aliphatic isocyanates, only is applied to the synthetic leather surface daub on a wall.The aliphatic polyurethane resin of mentioning among the present invention not only can be applied to the synthetic leather surface daub on a wall, also can produce for the synthesis of revolutionary cadre's method application wider.
CN101092538 has only adopted amine chain extender on synthesis technique in addition, but in actual production, amine chain extender and isocyanate reaction speed are very fast, come chain extension with 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 at the carbamate of flexibility not as hydroxyl in the polyvalent alcohol and isocyanate reaction generation, if all use the amine chain extension, the urea groups that generates too much will certainly affect the performance of product, the present invention adopts polyamine and polyvalent alcohol jointly as chainextender, not only steadily easily control of reflection, and polyvalent alcohol can by select different carbochain length with 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 purpose of xanthochromia, and anti-xanthochromia effect is general, can only reach 4 grades.The present invention adopts group aliphatic resin, itself just has natural anti-xanthochromia characteristic, need not to add oxidation inhibitor, and anti-xanthochromia reaches 5 grades, on the 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 purpose of the present invention provides a kind of Weak solvent aliphatic polyurethane resin for synthetic leather, adopt technical scheme of the present invention, the urethane resin that can synthesize different solid contents, different viscosity, different modulus, satisfy the needs that synthetic leather is produced, prepare have high thermal resistance, winter hardiness, non-stick property and the better synthetic leather product of color developing.Second purpose of the present invention provides above-mentioned Weak solvent aliphatic polyurethane resin for synthetic leather preparation method.
In order to realize first above-mentioned purpose, the present invention has adopted following technical scheme:
The use for synthetic leather weak solvent aliphatic polyurethane resin, this urethane resin is prepared by following component by weight percentage:
| The 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; The ratio of the amount of substance of vulcabond ester is 1:1.05 ~ 1:3.5 in the amount of the hydroxylated material in polyester or polyether alkylol cpd component and the small molecules polyvalent alcohol chain extender component and the aliphatic diisocyanate compound component; The amount of the hydroxylated material in polyester or polyether alkylol cpd component and the 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 the small molecules polyamine chainextender and the 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:
| The 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, the 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, the 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 benzene class such as toluene, dimethylbenzene etc., ester class such as ethyl acetate, butylacetate etc., ethers such as ethylene glycol monomethyl ether, propylene glycol monomethyl ether etc., alcohols such as methyl alcohol, ethanol, Virahol, propyl carbinol, isopropylcarbinol and composition thereof.
In order to realize second above-mentioned purpose, the present invention has adopted following technical scheme:
A kind ofly prepare above-mentioned use for synthetic leather weak solvent aliphatic polyurethane resin, the method comprises the steps:
(a) polyester or polyether polyols carry out vaccum dewatering drying 0.5～2h under 100 ℃;
(b) in reactor, add vulcabond, auxiliary agent, catalyzer, partial solvent and react needed part small molecules polyvalent alcohol chainextender in earlier stage, fully stir, at 60 ~ 90 ℃ of lower reaction 2 ~ 4h;
(c) add the required small molecules polyvalent alcohol chainextender of second step, at 60 ~ 90 ℃ of lower reaction 2 ~ 4h that continue;
(d) cool to 20 ~ 50 ℃, add remaining solvent, stir;
(e) slowly add the chainextender chain extension of small molecules binary amine, when system viscosity arrives 300cps ~ 300000cps viscosity, stop chain extension;
(f) cooling after the reaction, metering, packing.
The present invention adopts and does not contain the aliphatic diisocyanate of phenyl ring as raw material, synthetic product can xanthochromia under uviolizing, the progression of anti-the xanthochromia reaches 5 grades (according to the B method test of stipulating among the standard HG/T 3689-2001, test duration is 3 hours), and the anti-xanthochromia of common aromatic urethane resin only has 2 ~ 3 grades.Adopted simultaneously alcohol, the solvent of ethers has substituted deep-etching, the N that toxicity is larger, dinethylformamide, the butanone equal solvent, it is very little to the corrodibility of bass when synthetic leather is produced, feel and the characteristic that can keep bass, in actual production, with 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 the bass variable color to bass, and the synthetic leather wet method bass surface of coating product of the present invention does not significantly change.
By selecting different types of polyester and polyether glycol, can obtain the polyurethane products of different performance among the present invention, satisfy the requirement to performance of various synthetic leather.When selecting polyether glycol and polytetrahydrofuran polyvalent alcohol, the aliphatic polyurethane resin that obtains has good hydrolytic resistance and winter hardiness, and product has better mechanical property and temperature tolerance when selecting polyester polyol, then have two above characteristics when selecting polycaprolactone glycol and polycarbonate diol concurrently, but cost can be higher.
Do not contain the rigid structures such as aromatic ring in the aliphatic isocyanates structure of aliphatic polyurethane resin owing to employing, resin property is usually relatively poor usually, is difficult to satisfy 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.Preparation method according to Weak solvent aliphatic polyurethane resin for synthetic leather of the present invention, the urethane resin that can synthesize different solid contents, different viscosity, different modulus, satisfy the needs that synthetic leather is produced, prepare have high thermal resistance, winter hardiness, non-stick property and the better synthetic leather product of color developing.
Embodiment
Embodiment 1
With 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, 51 parts of 61 parts of IPDI, HDI, 10 parts of ethylene glycol, 1 part of dibutyl tin laurate, stir, be warmed up to 80 ℃, reaction 3h; The BDO that adds 12 parts, 80 ℃ are continued reaction 3h; Cool to 50 ℃, add after 150 parts of 200 parts of toluene, 200 parts of Virahols, ethyl acetate stir, slowly use 12 parts different Buddhist diketone diamines tackify, when viscosity is raised to 80000cps, stop to add different Buddhist diketone diamines; Continue to stir 30 minutes, then be 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; The BDO that adds 1 part, 0.5 part Diethylene Glycol 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, are slowly used 1.5 parts quadrol tackify, when viscosity is raised to 5000cps, stop to add quadrol; Continue to stir 30 minutes, then be 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, 19 parts of 83 parts of IPDI, H12MDI, 0.2 part of stannous octoate, stir, be warmed up to 90 ℃, reaction 3h; The BDO that adds 5 parts, 9 parts neopentyl glycol 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, are slowly used 13.8 parts IPDA tackify, when viscosity is raised to 3000cps, stop to add different Buddhist diketone diamines; Continue to stir 30 minutes, then be 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; 1,6 hexylene glycol that adds 46 parts continues anti-reaction 2h at 90 ℃; Cool to 50 ℃, add 100 parts of toluene, 100 parts of propyl carbinols, 100 parts of Virahols after stirring, are slowly used 53 parts different Buddhist diketone diamines tackify, when viscosity is raised to 150000cps, stop to add different Buddhist diketone diamines; Continue to stir 30 minutes, then be cooled to 30 ℃, discharging; Obtaining solid content is 50%, and modulus is 220kgf/cm
2Weak solvent aliphatic polyurethane resin.
Embodiment 5
Say the anti-xanthochromia characteristic that has in order to verify Weak solvent aliphatic polyurethane resin of the present invention, the resin that above-mentioned case is prepared is made the film that thickness is about 0.2mm, test its anti-yellowing property according to the B method of stipulating among the standard HG/T 3689-2001, the test duration is 3 hours.After testing, the resin anti-yellowing property of described case preparation has all reached 5 grade standards.
Claims (1)
1. the preparation method of a urethane resin is characterized in that the method comprises the steps:
1) 145 parts of polyneopentyl glycol adipate glycol are warmed up to 100 ℃, polyneopentyl glycol adipate glycol molecular weight 2000, the about 1h of vacuum hydro-extraction cools to 50 ℃;
2) 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;
3) 1,6 hexylene glycol that adds 46 parts continues reaction 2h at 90 ℃;
4) cool to 50 ℃, add 100 parts of toluene, 100 parts of propyl carbinols, 100 parts of Virahols after stirring, are slowly used 53 parts different Buddhist diketone diamines tackify, when viscosity is raised to 150000cps, stop to add different Buddhist diketone diamines;
5) continue to stir 30 minutes, then be cooled to 30 ℃, discharging; Obtaining solid content is 50%, and modulus is 220kgf/cm
2Weak solvent aliphatic polyurethane resin.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103435010A CN102850514A (en) | 2010-04-21 | 2010-04-21 | Polyurethane resin preparation method |
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|---|---|---|---|
| CN2012103435010A CN102850514A (en) | 2010-04-21 | 2010-04-21 | Polyurethane resin preparation method |
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| CN2010101524769A Division CN101824132B (en) | 2010-04-21 | 2010-04-21 | Weak solvent aliphatic polyurethane resin for synthetic leather and preparation method thereof |
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| CN102850514A true CN102850514A (en) | 2013-01-02 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103804627A (en) * | 2014-02-19 | 2014-05-21 | 合肥安利聚氨酯新材料有限公司 | Wet high-stripping polyurethane resin and preparation method thereof |
| CN111763474A (en) * | 2020-07-08 | 2020-10-13 | 中国科学院长春应用化学研究所 | High-adhesion environment-erosion-resistant polyurethane transparent coating and preparation and use methods thereof |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101016407A (en) * | 2007-01-26 | 2007-08-15 | 东莞市宏达聚氨酯有限公司 | Polyurethane resin composition and its preparing process |
| 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 |
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2010
- 2010-04-21 CN CN2012103435010A patent/CN102850514A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101016407A (en) * | 2007-01-26 | 2007-08-15 | 东莞市宏达聚氨酯有限公司 | Polyurethane resin composition and its preparing process |
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103804627A (en) * | 2014-02-19 | 2014-05-21 | 合肥安利聚氨酯新材料有限公司 | Wet high-stripping polyurethane resin and preparation method thereof |
| CN111763474A (en) * | 2020-07-08 | 2020-10-13 | 中国科学院长春应用化学研究所 | High-adhesion environment-erosion-resistant polyurethane transparent coating and preparation and use methods thereof |
| 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 |
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Application publication date: 20130102 |