CN103145930B - Preparation method of highly wear-resistant polyurethane resin for synthetic leather - Google Patents
Preparation method of highly wear-resistant polyurethane resin for synthetic leather Download PDFInfo
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Abstract
The invention relates to a preparation method of highly wear-resistant polyurethane resin for synthetic leather. The preparation method comprises the following steps: (I) heating and reacting polydiols, diisocyanate, dihydric alcohol chain extender, antioxidant, and catalyst in a solvent to prepare a prepolymer, wherein the diisocyanate is excessive; (II) adding terminator allyl alcohol for end group blocking to obtain macromolecules with -C=C structure-containing end group; (III) adding free radical polymerized initiator, function end group-containing micromolecular alkene for polymerization reaction; and (IV) adding free radical reaction terminator for terminating reaction, and regulating the viscosity to obtain the final product. The -C=C structure-containing end group is introduced into the tail end of the prepolymer, and then functionalized group-containing monomer is introduced into the tail end of the prepolymer, thereby functionally modifying the polyurethane in molecular level so as to achieve the purpose of improving the physical property of the polyurethane resin and enabling the produced synthetic leather to have better low-temperature, normal-temperature wear resistance property.
Description
Technical field
The invention belongs to synthetic leather field, relate to a kind of preparation method of use for synthetic leather high abrasion urethane resin.
Background technology
Urethane resin, due to molecular structure, the physicochemical property of its uniqueness, is widely used in synthetic leather field, spreads all over each fields such as clothes, footwear, automotive trim, daily living article, gos deep into the every aspect of people's life.Along with the progress of science and technology, the going deep into of research, every profession and trade has not met the existing product that routinizes for the use of polyurethane products, and high physical property urethane has become the main flow of development.Conventional polyurethanes product can give its hydrolysis, the advantage such as cold-resistant by the kind of polyvalent alcohol in adjustment building-up process and consumption, but room for promotion is limited, can not meet the demand for the higher field of Synthetic Leather performance requriements.Further, the polyvalent alcohol price that can play advantages such as promoting urethane hydrolysis, resist cold costly, is unfavorable for the use of producing on a large scale.The polyvalent alcohol of synthesis of polyurethane conventional is at present only limitted to polyester, polyethers, polycarbonate, polycaprolactone polyol, and kind is still comparatively single.In the polyurethane products course of processing, the performance index of Synthetic Leather can be promoted by adding different types of functionalization auxiliary agent, but have that auxiliary agent is difficult to mix, life-time service time auxiliary molecules be easy to lose efficacy with overflow, auxiliary agent has specific application area and the deficiencies such as resin that match.Therefore, the research and development for high physical property urethane resin have just become the task of top priority, particular molecular groups are introduced intramolecule and give the trend that Synthetic Leather specified property and course of processing situ systematic function auxiliary agent become development.Such as: the organosilicon containing terminal hydroxy group is introduced polyurethane molecular chain by (1) Chinese patent CN102604026A, improves glossiness and the transparency of Synthetic Leather product, improves feel and the surface slip of product simultaneously; (2) by Zhejiang Province's major scientific and technological program project " research and development of the novel PU synthetic leather of in-situ hybridization nano modification high physical property " (item number 2007C11100) of Sichuan University professor Fan Haojun hosting, the Five continents, Zhejiang Industrial Co., Ltd., Wenzhou University, Sichuan University's shared, the change of solidification liquid and water lotion ambient condition in traditional wet process technique is utilized to generate TiO at synthetic leather coating situ
2deng inorganic nano-particle, make synthetic leather have high ventilative, water vapour permeability, good antibacterial, mildew resistance and uvioresistant ageing-resistant performance, improve the grade of product.
Summary of the invention
The object of the invention is the preparation method proposing a kind of new use for synthetic leather high abrasion urethane resin, make synthetic leather have good low temperature, normal temperature wear resisting property.
The preparation method of this use for synthetic leather high abrasion urethane resin comprises the following steps:
(I) by poly-dihydric alcohol, vulcabond, di-alcohols chainextender, antioxidant, catalyzer in a solvent reacting by heating prepare performed polymer, wherein vulcabond is excessive;
(II) add terminator vinylcarbinol in the performed polymer be obtained by reacting in upper step and carry out end-block, obtain the macromole that end group contains-C=C structure;
(III) add radical polymerization initiator in the macromole be obtained by reacting in upper step, carry out polyreaction, functional modification urethane containing the small molecules alkene class of function end group;
(IV) add free radical reaction cessator termination reaction, and add solvent, adjustment viscosity obtains final product.
Wherein during the Ith step synthesis of polyurethane performed polymer, temperature of reaction controls at 75 ~ 80 DEG C, and the base polyurethane prepolymer for use as viscosity controller of synthesis is at 2.0 × 104 ~ 4.0 × 104MPaS/25 DEG C, and the mol ratio of isocyanate group and hydroxyl controls between 1.1:1 ~ 1.2:1; The end-block thing vinylcarbinol purity added in IIth step is more than 99.99%; IIIth step polyreaction nitrogen protection, temperature of reaction controls at 70 ~ 75 DEG C, containing 0.5% of the Mo Er amount≤isocyanic ester integral molar quantity of the small molecules alkene class of function end group; The final product viscosity controller of the IVth step is at 2.0 × 104 ~ 4.0 × 104MPaS/25 DEG C.
Method of the present invention is first by poly-dihydric alcohol and vulcabond, small molecules glycol chain extender reacts when vulcabond is excessive and generates performed polymer, and use vinylcarbinol as the terminator of performed polymer, group containing-C=C structure is introduced performed polymer end, again by radical polymerization by a small amount of vinyl cyanide, 3-chloro-1-propene, acrylamide, the monomer containing functionalization group such as vinylbenzene introduces performed polymer end, thus at molecular level functional modification urethane, reach the object of the physical property improving urethane resin, the synthetic leather made is made to have good low temperature, normal temperature wear resisting property.
Embodiment
The preparation method of this use for synthetic leather high abrasion urethane resin comprises the following steps:
(I) by poly-dihydric alcohol, vulcabond, di-alcohols chainextender, antioxidant and catalyzer in a solvent reacting by heating prepare performed polymer, wherein vulcabond is excessive;
(II) add vinylcarbinol in the performed polymer be obtained by reacting in upper step and carry out end-block, obtain the macromole that end group contains-C=C structure;
(III) add radical polymerization initiator, small molecules alkene class containing function end group in the macromole be obtained by reacting in upper step, carry out polyreaction, functional modification urethane;
(IV) add free radical reaction cessator, termination reaction, and add solvent, adjustment viscosity obtains final product, and also alternative adds auxiliary agent.
In the preparation method of this use for synthetic leather high abrasion urethane resin, poly-dihydric alcohol described in Ith step can be one or more in polyester diol, polyether Glycols or PCDL, the molecular weight of poly-dihydric alcohol can be 500 ~ 3000, and is linear molecule structure.The quality of poly-dihydric alcohol accounts for 75 ~ 85wt% of performed polymer total mass, described vulcabond can be 4, one or more in the aromatics vulcabond such as 4'-diphenylmethanediisocyanate, tolylene diisocyanate, described di-alcohols chainextender can be ethylene glycol, 1, one or more in the straight chain small molecules dibasic alcohol such as 4-butyleneglycol or 1,6-hexylene glycol; Initiator described in IIIth step can be azo or organo-peroxide type free base polymerization starter, is specially the initiators such as dibenzoyl peroxide, Diisopropyl azodicarboxylate, dilauroyl peroxide one or more.The described small molecules alkene class containing function end group can be vinyl cyanide, 3-chloro-1-propene, acrylamide or vinylbenzene.
In the preparation method of this use for synthetic leather high abrasion urethane resin, described in Ith step oxidation inhibitor can be 2,6-di-tert-butyl-4-methy phenol, described catalyzer is organic tin catalyzer, is specially one or more in the catalyzer such as stannous octoate, dibutyltin dilaurate.Described solvent can be that the one in dimethyl formamide, toluene, butanone or ethyl acetate is several; Terminator described in IVth step can be thiuram-disulfide type free base chain terminator.
In the preparation method of this use for synthetic leather high abrasion urethane resin, during the Ith step synthesis of polyurethane performed polymer, temperature of reaction can control at 75 ~ 80 DEG C, and the base polyurethane prepolymer for use as viscosity of synthesis can control 2.0 × 10
4~ 4.0 × 10
4mPaS/25 DEG C, the mol ratio of isocyanate group and hydroxyl can control between 1.1:1 ~ 1.2:1; The end-block thing vinylcarbinol purity added in IIth step can be more than 99.99%; IIIth step polyreaction nitrogen protection, temperature of reaction can control at 70 ~ 75 DEG C, and what add contains 0.5% of the Mo Er amount≤isocyanic ester integral molar quantity of the small molecules alkene class of function end group; IVth step final product viscosity can control 2.0 × 10
4~ 4.0 × 10
4mPaS/25 DEG C.
The specific operation process of the preparation method of this use for synthetic leather high abrasion urethane resin is as follows:
(1) dewatered under the vacuum condition of 90-110 DEG C by polyvalent alcohol, to reduce the generation of side reaction, dewatering time is greater than 5h, and the time of the polyvalent alcohol distance preparation feedback after dehydration is no more than 3h.
(2) add the solvent of polyvalent alcohol, chainextender, catalyzer and 30% proportioning in a kettle. by proportioning, keep soaking condition, until temperature reaches 65 DEG C, insulation 20min.
(3) be divided into by vulcabond and add in reactor 4 times, temperature controls at 75 ~ 80 DEG C, and the reaction times is 3 ~ 4h, and the mol ratio of isocyanate group and hydroxyl controls: 1.1:1 ~ 1.2:1, viscosity controller is 2.0 ~ 4.0 × 10
4mPaS/25 DEG C.
(4), after performed polymer generates, add the solvent of 50% in a kettle., and the vinylcarbinol monomer adding purity more than 99.99% stops to reaction, termination time 1 ~ 1.5 h, until termination reaction is complete.
(5) after termination reaction completes, pass into nitrogen in a kettle., and add radical polymerization initiator, small-numerator olefin class monomer containing functional group, carry out Raolical polymerizable, temperature controls at 70 ~ 75 DEG C, time 3 ~ 6h.
(6) after having reacted, add free radical reaction cessator termination reaction, and add remaining 20% solvent, adjustment product viscosity is to final claimed range, and solid content controls at 30wt%.After reaction terminates, selectivity adds the conven-tional adjuvants such as color developing conditioning agent, delustring conditioning agent.
(7) cool, obtain final product.
Final product polyurethane molecular of the present invention, its structure can be represented by the formula:
[r-C-C]
n2-O-(R
1-······R
n)-O-[C-C-r]
n1
R in formula
1, R
2, R
3r
nfor the structural unit of base polyurethane prepolymer for use as, n is natural number.R is functionalization group contained in vinyl monomer, and n1, n2 are the polymerization degree of later stage radical polymerization.
The present invention is by linking base polyurethane prepolymer for use as and small-numerator olefin under molecularity, make in polyurethane molecular, to the addition of the segment containing functionalization group, avoid the problem of the various poor compatibility occurred because additive and polyurethane molecular polarity difference are large, and selected its rigidity of functionalization group, toughness are all comparatively excellent, can resist the effect of the external force put on polyurethane material preferably; In addition auxiliary agent in drying course is there will not be to volatilize all kinds of technical barriers caused.This kind of polyurethane material remains the performance characteristics of conventional polyurethanes material, and imparts the good low temperature of material, normal temperature wear resisting property.
To be described further the present invention by specific embodiment below.
Embodiment 1:
(a) proportioning raw materials
| Raw material | Title | Amount of substance/quality |
| Poly-dihydric alcohol | PTMG (polyether Glycols, molecular weight 2000) | 0.075mol/150g |
| Vulcabond | MDI (4,4'-diphenylmethanediisocyanate) | 0.132mol/33.03g |
| Chainextender | Isosorbide-5-Nitrae-BG (Isosorbide-5-Nitrae butyleneglycol) | 0.045mol/4.05g |
| Oxidation inhibitor | 2,6 di tert butyl 4 methyl phenol | 0.25g |
| Catalyzer | Stannous octoate | 0.02g |
| Solvent | DMF (dimethyl formamide) | 438.67g |
| Terminator | Vinylcarbinol | 0.012mol/0.70g |
| Protective atmosphere | Nitrogen | Circulation |
| Free radical reaction initiator | Dilauroyl peroxide | 0.0018g |
| Containing the small molecules alkene class of function end group | Vinyl cyanide | 0.037g |
| Free radical reaction cessator | Tetramethyl-thiuram disulfide | 0.0018g |
| Auxiliary agent | Color spreading agent | 0.2g |
The mol ratio of isocyanate group and hydroxyl is 1.1:1.
(b) preparation process
Dibasic alcohol is dewatered under the vacuum condition of 110 DEG C, dewatering time 6h.
Add PTMG 150g, chainextender Isosorbide-5-Nitrae-BG 4.05g, oxidation inhibitor 2,6 di tert butyl 4 methyl phenol 0.25g, solvent DMF 131.6g in a kettle., be warming up to 65 DEG C, insulation 20min.4,4'-diphenylmethanediisocyanate is divided into 4 times, and each 8.2575g adds in reactor, and temperature controls at 75 DEG C, and the reaction times is 4h, adds the sub-tin 0.02g of octoate catalyst after dropping into MDI the 2nd time.After performed polymer generates, sampling 100g is quickly cooled to 25 DEG C and tested viscosity value, and result is 3.5 × 10
4mPaS.The solvent DMF 219.34g (50%) added in reactor after performed polymer generates, after stirring, after passing into protection gas nitrogen 20min, adds terminator vinylcarbinol 0.70g and reacts 1.5h in reactor.Stop terminating to add free radical reaction initiator dilauroyl peroxide 0.0018g in backward reactor, add vinyl cyanide 0.037g after 0.5h, temperature controls at 75 DEG C, reaction times 4h.After having reacted, add free radical reaction cessator tetramethyl-thiuram disulfide 0.0018g termination reaction, and add solvent DMF 87.73g (20%) and color spreading agent 0.2g, obtain the product 526g that final solid content is 30wt% after stirring, being cooled to 25 DEG C, to record viscosity be 3.1 × 10
4mPaS.
Embodiment 2:
(a) proportioning raw materials
| Raw material | Title | Amount of substance/quality |
| Poly-dihydric alcohol | Polyester diol (molecular weight 2000) | 0.075mol/150g |
| Vulcabond | MDI (4,4'-diphenylmethanediisocyanate) | 0.149mol/37.41g |
| Chainextender | Isosorbide-5-Nitrae-BG (Isosorbide-5-Nitrae butyleneglycol) | 0.055mol/4.96g |
| Oxidation inhibitor | 2,6 di tert butyl 4 methyl phenol | 0.28g |
| Catalyzer | Stannous octoate | 0.02g |
| Solvent | DMF (dimethyl formamide) | 453.53g |
| Terminator | Vinylcarbinol | 0.019mol/1.10g |
| Protective atmosphere | Nitrogen | Circulation |
| Free radical reaction initiator | Dilauroyl peroxide | 0.0041g |
| Containing the small molecules alkene class of function end group | 3-chloro-1-propene | 0.082g |
| Free radical reaction cessator | Tetramethyl-thiuram disulfide | 0.0041g |
| Auxiliary agent | Color development auxiliary agent | 0.2g |
The mol ratio of isocyanate group and hydroxyl is 1.15:1.
(b) preparation process
Dibasic alcohol is dewatered under the vacuum condition of 110 DEG C, dewatering time 6h.
Add polyester diol 150g, chainextender Isosorbide-5-Nitrae-BG 4.96g, oxidation inhibitor 2,6 di tert butyl 4 methyl phenol 0.28g, solvent DMF 136.06g in a kettle., be warming up to 65 DEG C, insulation 20min.4,4'-diphenylmethanediisocyanate is divided into 4 times, and each 9.35g adds in reactor, and temperature controls at 75 DEG C, and the reaction times is 4h, adds the sub-tin 0.02g of octoate catalyst after dropping into MDI the 2nd time.After performed polymer generates, sampling 100g is quickly cooled to 25 DEG C and records viscosity number is 3.3 × 10
4mPaS.The solvent DMF 226.77g (50%) added in reactor after performed polymer generates.After stirring, after passing into protection gas nitrogen 20min in reactor, add terminator vinylcarbinol 1.10g and react 1.5h.Stop terminating to add free radical reaction initiator dilauroyl peroxide 0.0041g in backward reactor, add 3-chloro-1-propene 0.082g after 0.5h, temperature controls at 75 DEG C, reaction times 4h.After having reacted, add free radical reaction cessator tetramethyl-thiuram disulfide 0.0041g termination reaction, and add solvent DMF 90.71g (20%) and color spreading agent 0.2g, obtain the product 547g that final solid content is 30wt% after stirring, being cooled to 25 DEG C, to record viscosity be 2.8 × 10
4mPaS.
Embodiment 3:
(a) proportioning raw materials
The mol ratio of isocyanate group and hydroxyl is 1.2:1.
(b) preparation process
Dibasic alcohol is dewatered under the vacuum condition of 110 DEG C, dewatering time 6h.
Add polyester diol 150g, chainextender Isosorbide-5-Nitrae-BG 4.05g, oxidation inhibitor 2,6 di tert butyl 4 methyl phenol 0.31g, solvent DMF 139.50g in a kettle., be warming up to 65 DEG C, insulation 20min.4,4'-diphenylmethanediisocyanate is divided into 4 times, and each 10.81g adds in reactor, and temperature controls at 75 DEG C, and the reaction times is 4h, adds the sub-tin 0.02g of octoate catalyst after dropping into MDI the 2nd time.After performed polymer generates, sampling 100g is quickly cooled to 25 DEG C and tested viscosity value, and result is 3.2 × 10
4mPaS.The solvent DMF 232.51g (50%) added in reactor after performed polymer generates.After stirring, after passing into protection gas nitrogen 20min in reactor, add terminator vinylcarbinol 1.39g and react 1.5h.Stop terminating to add free radical reaction initiator dilauroyl peroxide 0.0003g in backward reactor, add acrylamide 0.05g after 0.5h, temperature controls at 75 DEG C, reaction times 4h.After having reacted, add free radical reaction cessator tetramethyl-thiuram disulfide 0.0003g termination reaction, and add solvent DMF 93.00g (20%) and color spreading agent 0.2g, obtain the product 564g that final solid content is 30wt% after stirring, being cooled to 25 DEG C, to record viscosity be 2.6 × 10
4mPaS.
Embodiment 4:
(a) proportioning raw materials
The mol ratio of isocyanate group and hydroxyl is 1.14:1.
(b) preparation process
Dibasic alcohol is dewatered under the vacuum condition of 110 DEG C, dewatering time 6h.
Add polyester diol 150g, chainextender EG 3.72g, oxidation inhibitor 2,6 di tert butyl 4 methyl phenol 0.18g, solvent DMF 127.75g in a kettle., be warming up to 65 DEG C, insulation 20min.Tolylene diisocyanate is divided into 3 times, each 8.93g adds in reactor, and temperature controls at 75 DEG C, and the reaction times is 4h, adds the sub-tin 0.02g of octoate catalyst after dropping into TDI the 2nd time.After performed polymer generates, sampling 100g is quickly cooled to 25 DEG C and tested viscosity value, and result is 3.7 × 10
4mPaS.Solvent DMF 212.96g (50%) is added in reactor after performed polymer generates.After stirring, after passing into protection gas nitrogen 20min in reactor, add terminator vinylcarbinol 1.10g and react 1.5h.Stop terminating to add free radical reaction initiator dilauroyl peroxide 0.0067g in backward reactor, add vinylbenzene 0.134g after 0.5h, temperature controls at 75 DEG C, reaction times 4h.After having reacted, add free radical reaction cessator tetramethyl-thiuram disulfide 0.0067g termination reaction, and add solvent DMF 85.16g (20%) and color spreading agent 0.2g, obtain the product 507g that final solid content is 30wt% after stirring, being cooled to 25 DEG C, to record viscosity be 3.3 × 10
4mPaS.
Embodiment 5:
(a) proportioning raw materials
The mol ratio of isocyanate group and hydroxyl is 1.16:1.
(b) preparation process
Dibasic alcohol is dewatered under the vacuum condition of 110 DEG C, dewatering time 6h.
Add polyester diol 150g, chainextender EG 1.55g, BG 2.25g oxidation inhibitor 2,6 di tert butyl 4 methyl phenol 0.22g, solvent DMF 108.94g (50wt%) in a kettle., be warming up to 65 DEG C, insulation 20min.Add in reactor by tolylene diisocyanate 12.18g, temperature controls at 75 DEG C, and the reaction times is 2h, then residue MDI is divided into 2 times, and each 9.375g adds in reactor, and the reaction times is 4h, adds the sub-tin 0.02g of octoate catalyst after dropping into TDI the 2nd time.After performed polymer generates, sampling 100g is quickly cooled to 25 DEG C and tested viscosity value, and result is 3.5 × 10
4mPaS.Solvent DMF 108.94g (50wt%), solvent MEK 108.94g (50wt%) is added in reactor after performed polymer generates.After stirring, after passing into protection gas nitrogen 20min in reactor, add terminator vinylcarbinol 1.45g and react 1.5h.Stop terminating to add free radical reaction initiator dilauroyl peroxide 0.0077g in backward reactor, add vinyl cyanide 0.08g, 3-chloro-1-propene 0.075g after 0.5h, temperature controls at 75 DEG C, reaction times 4h.After having reacted, add free radical reaction cessator tetramethyl-thiuram disulfide 0.0077g termination reaction, and add solvent MEK 108.94g (50wt%) and color spreading agent 0.2g, obtain the product 521g that final solid content is 30wt% after stirring, being cooled to 25 DEG C, to record viscosity be 3.1 × 10
4mPaS.
Embodiment 6:
(a) proportioning raw materials
The mol ratio of isocyanate group and hydroxyl is 1.12:1.
(b) preparation process
Dibasic alcohol is dewatered under the vacuum condition of 110 DEG C, dewatering time 6h.
Add polyester diol 150g, chainextender EG 2.48g, oxidation inhibitor 2,6 di tert butyl 4 methyl phenol 0.21g, solvent DMF 123.82g in a kettle., be warming up to 65 DEG C, insulation 20min.Tolylene diisocyanate is divided into 3 times, each 7.47g adds in reactor, and temperature controls at 75 DEG C, and the reaction times is 4h, adds the sub-tin 0.02g of octoate catalyst after dropping into TDI the 2nd time.After performed polymer generates, sampling 100g is quickly cooled to 25 DEG C and tested viscosity value, and result is 3.8 × 10
4mPaS.The solvent DMF 206.37g of 50% is added in reactor after performed polymer generates.After stirring, after passing into protection gas nitrogen 20min in reaction ax, add terminator vinylcarbinol 0.81g and react 1.5h.Stop terminating to add free radical reaction initiator dilauroyl peroxide 0.002g in backward reactor, add vinyl cyanide 0.018g, acrylamide 0.023g after 0.5h, temperature controls at 75 DEG C, reaction times 4h.After having reacted, add free radical reaction cessator tetramethyl-thiuram disulfide 0.002g termination reaction, and add 20% solvent DMF 82.58g and color spreading agent 0.2g, obtain the product 488g that final solid content is 30wt% after stirring, being cooled to 25 DEG C, to record viscosity be 3.3 × 10
4mPaS.
The urethane of above-described embodiment gained is made sample, carries out normal temperature and low temperature wear resistance can be tested.Preparation and the testing method of sample are as follows:
100 parts of urethane are added 3 parts of black powder, after strong stirring 8min, in being directly applied on soft white nanometer leather end embryo, thickness 0.15mm, and be placed in 120 DEG C of baking ovens and dry completely.Cut the round sheet sample of radius 5cm for wear-resisting test.Test adopts circular grinding wheel (material is the grains of sand) to contact with disc-shaped test specimens, load-carrying 750g, rotating speed 60 ~ 70rpm, until surface layer urethane breaks.Utilize analyzer room's air-conditioning to carry out temperature control during test, reach after probe temperature until temperature and carry out wear-resisting test again after 2h.Be completed rear calculating disc-shaped test specimens the coefficient of number as measurement synthetic leather wear resisting property of turn-taking.
Synthesized by each embodiment, urethane the performance test results is as following table:
The normal temperature wear resistance (25 DEG C) of conventional polyurethanes is 800-1000 circle, 10 DEG C of low temperature wear resistance are 500-700 circle, 5 DEG C of low temperature wear resistance <300 enclose, and compared with conventional products, normal temperature, the low temperature wear resistance of the sample of 6 embodiment gained all obviously improve.
Claims (4)
1. a preparation method for use for synthetic leather high abrasion urethane resin, is characterized in that comprising the following steps:
(I) by poly-dihydric alcohol, vulcabond, di-alcohols chainextender, antioxidant, catalyzer in a solvent reacting by heating prepare performed polymer, wherein vulcabond is excessive;
(II) add terminator vinylcarbinol in the performed polymer be obtained by reacting in upper step and carry out end-block, obtain the macromole that end group contains-C=C structure;
(III) add radical polymerization initiator in the macromole be obtained by reacting in upper step, carry out polyreaction, functional modification urethane containing the small molecules alkene class of function end group;
(IV) add free radical reaction cessator termination reaction, and add solvent, adjustment viscosity obtains final product; Wherein during the Ith step synthesis of polyurethane performed polymer, temperature of reaction controls at 75 ~ 80 DEG C, and the base polyurethane prepolymer for use as viscosity controller of synthesis is 2.0 × 10
4~ 4.0 × 10
4mPaS/25 DEG C, the mol ratio of isocyanate group and hydroxyl controls between 1.1:1 ~ 1.2:1; The end-block thing vinylcarbinol purity added in IIth step is more than 99.99%; IIIth step polyreaction nitrogen protection, temperature of reaction controls at 70 ~ 75 DEG C, containing 0.5% of the Mo Er amount≤isocyanic ester integral molar quantity of the small molecules alkene class of function end group; The final product viscosity controller of the IVth step is at 2.0 × 104 ~ 4.0 × 104MPaS/25 DEG C.
2. the preparation method of use for synthetic leather high abrasion urethane resin as claimed in claim 1, it is characterized in that the poly-dihydric alcohol described in the Ith step is one or more in polyester diol, polyether Glycols or PCDL, the molecular weight of poly-dihydric alcohol is 500 ~ 3000, the quality of poly-dihydric alcohol accounts for 75 ~ 85wt% of performed polymer total mass, described vulcabond is one or more in aromatics vulcabond, and described di-alcohols chainextender is one or more in straight chain small molecules dibasic alcohol; Initiator described in IIIth step is azo or organo-peroxide type free base polymerization starter; The described small molecules alkene class containing function end group is vinyl cyanide, 3-chloro-1-propene, acrylamide or vinylbenzene.
3. the preparation method of use for synthetic leather high abrasion urethane resin as claimed in claim 2, is characterized in that described vulcabond is the one of 4,4'-diphenylmethanediisocyanate or tolylene diisocyanate or two kinds; Described di-alcohols chainextender is one or more in ethylene glycol, BDO or 1,6-hexylene glycol.
4. the preparation method of use for synthetic leather high abrasion urethane resin as claimed in claim 3, it is characterized in that described in the Ith step oxidation inhibitor be 2,6-di-tert-butyl-4-methy phenol, described catalyzer is organic tin catalyzer, and described solvent is that the one in dimethyl formamide, toluene, butanone or ethyl acetate is several; Free radical reaction cessator described in IVth step is thiuram-disulfide type free base chain terminator.
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| CN101481443A (en) * | 2009-01-23 | 2009-07-15 | 华南理工大学 | Polyurethane-polyacrylacid ester interpenetrating network polymer, preparation and use thereof |
| CN101792570A (en) * | 2010-02-10 | 2010-08-04 | 汤汉良 | Hydroxyl-containing crylic acid polyurethane aqueous dispersion body and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481443A (en) * | 2009-01-23 | 2009-07-15 | 华南理工大学 | Polyurethane-polyacrylacid ester interpenetrating network polymer, preparation and use thereof |
| CN101792570A (en) * | 2010-02-10 | 2010-08-04 | 汤汉良 | Hydroxyl-containing crylic acid polyurethane aqueous dispersion body and application |
Non-Patent Citations (1)
| Title |
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| 双键单封端聚氨酯丙烯酸酯大分子单体的合成及表征;夏宇正等;《现代化工》;20090531;第29卷(第5期);46-49页 * |
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