CN111363343A - Dry-process fabric resin for high-temperature-resistant protein PU leather and preparation method thereof - Google Patents
Dry-process fabric resin for high-temperature-resistant protein PU leather and preparation method thereof Download PDFInfo
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- CN111363343A CN111363343A CN202010240550.6A CN202010240550A CN111363343A CN 111363343 A CN111363343 A CN 111363343A CN 202010240550 A CN202010240550 A CN 202010240550A CN 111363343 A CN111363343 A CN 111363343A
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- isocyanate
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- 239000011347 resin Substances 0.000 title claims abstract description 57
- 229920005989 resin Polymers 0.000 title claims abstract description 57
- 239000010985 leather Substances 0.000 title claims abstract description 37
- 238000001035 drying Methods 0.000 title claims abstract description 33
- 239000004744 fabric Substances 0.000 title claims abstract description 33
- 102000004169 proteins and genes Human genes 0.000 title claims abstract description 23
- 108090000623 proteins and genes Proteins 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 14
- 239000004970 Chain extender Substances 0.000 claims abstract description 13
- 239000012948 isocyanate Substances 0.000 claims abstract description 13
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 13
- 239000000945 filler Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 9
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 9
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 13
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 13
- RWANVDVCJSCLIR-UHFFFAOYSA-N CC=CC.C(CCCCCCCCC(=O)O)(=O)O Chemical compound CC=CC.C(CCCCCCCCC(=O)O)(=O)O RWANVDVCJSCLIR-UHFFFAOYSA-N 0.000 claims description 6
- DIMIZNCAUQVNHV-UHFFFAOYSA-N CC=CC.C(CCCCC(=O)O)(=O)O Chemical compound CC=CC.C(CCCCC(=O)O)(=O)O DIMIZNCAUQVNHV-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 3
- 229920002301 cellulose acetate Polymers 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 43
- 239000004814 polyurethane Substances 0.000 description 41
- 239000004322 Butylated hydroxytoluene Substances 0.000 description 10
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 10
- 229940095259 butylated hydroxytoluene Drugs 0.000 description 10
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000002649 leather substitute Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000004902 Softening Agent Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- ALSBIHMPXBVFAO-UHFFFAOYSA-N butane-2,3-diol decanedioic acid Chemical compound C(CCCCCCCCC(=O)O)(=O)O.CC(C(C)O)O ALSBIHMPXBVFAO-UHFFFAOYSA-N 0.000 description 2
- VVWMIGDZTWDLTH-UHFFFAOYSA-N butane-2,3-diol hexanedioic acid Chemical compound C(CCCCC(=O)O)(=O)O.CC(C(C)O)O VVWMIGDZTWDLTH-UHFFFAOYSA-N 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000003161 proteinsynthetic effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/06—Polyurethanes from polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3271—Hydroxyamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The scheme relates to a dry-process fabric resin for high-temperature-resistant protein PU leather and a preparation method thereof, wherein the preparation method comprises the following steps: putting polyester polyol, DMF, antioxidant BHT and phosphoric acid into a reaction bottle, uniformly stirring, adding isocyanate, and reacting at 70-80 ℃ for 1.5 h; adding a chain extender into a reaction bottle, uniformly stirring, adding isocyanate, reacting and tackifying at 70-80 ℃ until the viscosity of the system reaches 8-14 ten thousand cps/DEG C; and adding methanol for end capping after the tackifying reaction is finished, adding the filler and the auxiliary agent after the end capping is carried out for 1h, and then, continuously stirring for 1h and cooling the package material. The dry-method fabric resin prepared by the scheme has softer hand feeling than the existing dry-method fabric, and the PU leather prepared by the dry-method fabric resin has good surface smoothness and is not sticky; the softening point is high, and the high temperature resistance is good; the synthesis process is simple, the cost performance is high, and the market potential is huge.
Description
Technical Field
The invention relates to the field of dry fabric resin for protein PU leather, in particular to dry fabric resin for high-temperature-resistant protein PU leather and a preparation method thereof.
Background
The rise of animal protection connotation promotes the development of the synthetic leather industry, the traditional PVC artificial leather is mainly suitable for low-grade products due to stiff hand feeling, and the PU synthetic leather can prepare hand feeling with different air lattices by virtue of microphase separation between soft and hard sections. Compare in airtight PVC synthetic leather, the PU synthetic leather is changeed and receives people's favor. PU leather can be classified into wet-process bass and dry-process coatings depending on the method of preparation. The wet base is prepared by adding inorganic filler such as wood powder, calcium powder, diatomite and kaolin into PU resin, coating or impregnating the PU resin on the surface of base cloth, solidifying, pressing water, drying and the like, and the artificial leather with porous interior, flat surface, different hand feeling and similar physical property to leather is prepared. The prepared wet-process bass is only a semi-finished product of PU leather, and if a finished product of the PU leather is prepared, the finished product of the PU leather needs to be subjected to procedures of dry veneering, graining, embossing, buffing, digital printing and the like. The dry-process fabric is prepared by mixing and defoaming the dry-process PU resin and the color flake solvent, coating the mixture on the surface of release paper, drying the release paper in an oven, coating a dry-process adhesive on the release paper, adhering wet-process bass, compacting and drying the mixture, and then stripping the mixture from the surface of the release paper to obtain the complete PU leather. PU leather can be classified into rebound type, soft-elastic type, soft-cotton type, velvet type, plump type and protein type according to the hand feeling difference. Each type of PU leather needs to be matched with the corresponding wet resin and dry adhesive for use. For example, the PU leather prepared by the soft-cotton wet method bass matching with the hard dry method fabric can lose the soft-cotton style. Among the PU leathers, the protein PU leather is often applied to high-grade leather products, and has better economic benefit. However, the dry-process fabric resin requirements of the protein PU leather are very strict, such as heat resistance and protein hand feeling.
The softer the normal dry-process fabric resin hand feeling, the more sticky the prepared PU leather surface is, the more easily the PU leather is stained with ash, and the softer the resin is, the poorer the heat resistance is. And the ultra-soft PU leather needs to be subjected to graining treatment after the preparation, and when the graining is carried out, the PU leather is easily adhered together if the surface layer is sticky by a dry method, so that the manpower and material resources during the production of downstream leather factories are increased. Therefore, how to prepare the dry-process fabric resin with ultra-soft hand feeling (protein hand feeling), good high temperature resistance and non-stick PU leather surface is always a hotspot and difficulty of research in the PU leather field.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides dry-process fabric resin for high-temperature-resistant protein PU leather and a preparation method thereof, so that the prepared product has the functions of excellent protein hand feeling and heat resistance, and smooth and dustproof surface.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a preparation method of dry-process fabric resin for high-temperature-resistant protein PU leather comprises the following steps:
1) putting polyester polyol, DMF (N, N-dimethylformamide), antioxidant BHT and phosphoric acid into a reaction bottle, uniformly stirring, adding isocyanate, and reacting at 70-80 ℃ for 1.5 h;
2) adding a chain extender into a reaction bottle, uniformly stirring, adding isocyanate, reacting and tackifying at 70-80 ℃ until the viscosity of the system reaches 8-14 ten thousand cps/DEG C;
3) and adding methanol for end capping after the tackifying reaction is finished, adding the filler and the auxiliary agent after the end capping is carried out for 1h, and then, continuously stirring for 1h and cooling the package material.
Preferably, in the production method, the polyester polyol is at least one selected from the group consisting of poly (methyl propylene adipate) glycol, poly (methyl propylene sebacate) glycol, and poly (methyl propylene sebacate) glycol.
Preferably, in the preparation method, the R value of the isocyanate in the step 1) is 0.7.
Preferably, in the preparation method, the R value of the isocyanate in the step 2) is 1.
Preferably, in the preparation method, the chain extender is monoethanolamine.
Preferably, the method of manufacturing, wherein the filler is selected from SAN resin, PAN resin, ABS resin, cellulose acetate or a combination thereof.
Preferably, in the preparation method, the auxiliary is an organosilicon softening agent.
The dry-process fabric resin for the high-temperature-resistant protein PU leather prepared by the preparation method.
The technical difficulty of the scheme is that when the molecular weight of polyester polyol used in the preparation of dry-process fabric resin is large, ultra-soft hand feeling is easily obtained, but the surface of the prepared PU leather is easily sticky and dust-absorbing, and the heat resistance is poor. According to the scheme, researches show that the high-molecular-weight polyester polyol containing the lateral methyl groups can effectively reduce the acting force among resins due to the existence of larger steric hindrance, and can easily obtain ultra-soft hand feeling when being used for preparing protein PU dry-process fabric resin. In order to further improve the heat resistance of the resin, monoethanolamine used as a chain extender is used on the basis of a prepolymerization process in the invention. The PU dry-process surface layer resin prepared by taking monoethanolamine as a chain extender has good heat resistance. After the synthetic reaction, the filling resin and the auxiliary agent are added after the resin is blocked, the filling resin can effectively reduce the cohesiveness of a dry-process surface layer, and the auxiliary agent is filled among molecular chains of the resin, so that the cohesive energy of the resin is effectively reduced, and further, an ideal protein hand feeling is obtained.
The product prepared by the method has the functions of protein handfeel, excellent heat resistance and smooth and dustproof surface, and the dry-method fabric resin has the advantages of simple synthesis process, convenient operation, low raw material cost and high product added value, and is particularly suitable for preparing earphone cover leather in special occasions.
The polyester polyol in the present invention includes, but is not limited to, at least one of poly (methyl propylene adipate) glycol (molecular weight 6000), poly (methyl propylene adipate) glycol (molecular weight 8000), poly (methyl propylene sebacate) glycol (molecular weight 6000), or poly (methyl propylene sebacate) glycol (molecular weight 8000). The dry-process fabric resin prepared by the invention has heat resistance, so a polyether structure cannot be selected, ether bonds are easily decomposed under a heated condition, the aging of the PU resin is accelerated, and the service life of the PU resin is shortened. The methyl propylene glycol in the polyester polyol contains a side methyl structure, has a larger steric hindrance effect, and can effectively reduce the cohesion among PU resin molecules, so that the prepared leather-like hand feeling is softer. Meanwhile, the side methyl structure is helpful for enhancing the heat resistance, mould resistance and hydrolysis resistance of the resin.
The antioxidant BHT in the invention is mainly used for preventing the resin from turning red due to the fact that the resin is heated locally and greatly in the preparation process of the resin. The phosphoric acid serves to prevent self-polymerization between isocyanates and to reduce the probability of side reactions occurring.
The chain extender used in the present invention is monoethanolamine; the monoethanolamine contains a hydroxyl group and an amino group respectively, so that the resin is prevented from gelling due to the excessively fast reaction rate of the diethanolamine; and the dry-process fabric resin prepared from the monoethanolamine has better heat resistance, and the reaction rate of the monoethanolamine is slower than that of the diethanolamine, but is obviously much faster than that of micromolecular dihydric alcohol. Therefore, the step 1) of the present invention uses a prepolymerization process, mainly to prevent monoethanolamine from reacting too fast to form a continuous urea bond structure in the resin to cause gelation.
After the reaction is finished, the filling material and the auxiliary agent are added. The molecular weight of the selected polyester polyol is 6000-8000, and the polyurethane resin prepared from the polyester polyol has good bonding property. However, when the fabric is applied to the dry-process fabric, the surface of the dry-process fabric is easily sticky, and dust is easily adsorbed to influence the appearance of the fabric. Therefore, the purpose of adding the filler in the invention is to reduce the viscosity of the surface of the resin, so that the surface is smooth and does not adsorb dust. The auxiliary agent has the function of reducing the acting force among the resins, so that the prepared resin has softer hand feeling and is close to the style of protein synthetic leather.
The invention has the beneficial effects that: 1) the hand feeling is softer than that of the existing dry-method fabric; 2) the prepared PU leather has good surface smoothness and is not sticky with ash; 3) the softening point is high, and the high temperature resistance is good; 4) the synthesis process is simple, the cost performance is high, and the market potential is huge.
Detailed Description
The technical solutions of the present invention are described clearly and completely below, and it is obvious that the described embodiments are some, not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
First, preparation process
Firstly, weighing a certain amount of polyester polyol, putting the polyester polyol into a reaction bottle, dehydrating the polyester polyol for 2 hours at the negative pressure of 110 ℃, and testing that the water content in the polyol is below 300ppm to be qualified. Adding a proper amount of solvent DMF, antioxidant BHT and phosphoric acid into a reaction bottle, stirring uniformly, adding isocyanate (R is 0.7) and reacting for 1.5h at 70-80 ℃. Adding a solvent and a chain extender into a reaction bottle, uniformly stirring, adding isocyanate (R ═ 1) into the reaction bottle, reacting at 70-80 ℃, and thickening, wherein DMF can be used for diluting properly. And (3) after the reaction is finished, sealing the end by using methanol, adding the filler and the auxiliary agent after the end is sealed for 1h, continuously stirring for 1h, and cooling the package material. The viscosity of the obtained resin is 8-14 ten thousand (cps/DEG C), and the solid content is 30%.
Example 1: accurately weighing 300g of poly (methyl propylene glycol adipate) glycol (with the molecular weight of 6000) in a reaction bottle, dehydrating for 2h at the temperature of 110 ℃ under negative pressure, testing that the water content is qualified when the water content is below 300ppm, and simultaneously adding 300g of DMF (dimethyl formamide), 0.2g of antioxidant BHT and 0.003g of phosphoric acid and fully and uniformly stirring. And then 8.75g of MDI (set R value to be 0.7) is added into the reaction bottle and is uniformly stirred to react for 1.5h at the temperature of 70-80 ℃, 13g of DMF and chain extender monoethanolamine are added into the reaction bottle, stirring is continued for 30min, and then 56.9g of MDI (set R value to be 1) is added to react and tackify at the temperature of 70-80 ℃. DMF can be properly added in batches for dilution in the tackifying process. And (3) after the reaction is finished, sealing the end by using methanol, adding 15g of filler SAN resin and 4g of organic silicon softening agent after the end is sealed for 1h, continuously stirring for 1h, and cooling the packed material. The viscosity of the obtained resin is 8-14 ten thousand (cps/DEG C), and the solid content is 30%.
Example 2: accurately weighing 300g of poly (methyl propylene glycol adipate) (molecular weight 8000) into a reaction bottle, dehydrating for 2h at 110 ℃ under negative pressure, testing that the water content is qualified when the water content is below 300ppm, and simultaneously adding 300g of DMF (dimethyl formamide), 0.2g of antioxidant BHT (butylated hydroxytoluene) and 0.003g of phosphoric acid, and fully and uniformly stirring. And then 6.56g of MDI (set R value to be 0.7) is added into the reaction bottle and is uniformly stirred to react for 1.5h at the temperature of 70-80 ℃, then 13g of DMF and chain extender monoethanolamine are added into the reaction bottle, stirring is continued for 30min, and then 56.02g of MDI (set R value to be 1) is added to react and tackify at the temperature of 70-80 ℃. DMF can be properly added in batches for dilution in the tackifying process. And (3) after the reaction is finished, sealing the end by using methanol, adding 15g of filler PAN resin and 4g of organic silicon softening agent after the end is sealed for 1h, continuously stirring for 1h, and cooling the packed material. The viscosity of the obtained resin is 8-14 ten thousand (cps/DEG C), and the solid content is 30%.
Example 3: accurately weighing 300g of poly (methyl propylene glycol sebacate) glycol (molecular weight 6000) in a reaction bottle, dehydrating for 2h at 110 ℃ under negative pressure, testing that the water content is qualified below 300ppm, and simultaneously adding 300g of DMF (dimethyl formamide), 0.2g of antioxidant BHT (butylated hydroxytoluene) and 0.003g of phosphoric acid, and fully and uniformly stirring. And then 8.75g of MDI (set R value to be 0.7) is added into the reaction bottle and is uniformly stirred to react for 1.5h at the temperature of 70-80 ℃, 13g of DMF and chain extender monoethanolamine are added into the reaction bottle, stirring is continued for 30min, and then 56.9g of MDI (set R value to be 1) is added to react and tackify at the temperature of 70-80 ℃. DMF can be properly added in batches for dilution in the tackifying process. And (3) after the reaction is finished, sealing the end by using methanol, adding 15g of ABS resin filler and 4g of organosilicon softening agent after the end is sealed for 1h, continuously stirring for 1h, and cooling the packed material. The viscosity of the obtained resin is 8-14 ten thousand (cps/DEG C), and the solid content is 30%.
Example 4: accurately weighing 300g of poly (methyl propylene glycol sebacate) glycol (molecular weight 8000) in a reaction bottle, dehydrating for 2h at 110 ℃ under negative pressure, testing that the water content is qualified below 300ppm, and simultaneously adding 300g of DMF (dimethyl formamide), 0.2g of antioxidant BHT (butylated hydroxytoluene) and 0.003g of phosphoric acid, and fully and uniformly stirring. And then 6.56g of MDI (set R value to be 0.7) is added into the reaction bottle and is uniformly stirred to react for 1.5h at the temperature of 70-80 ℃, then 13g of DMF and chain extender monoethanolamine are added into the reaction bottle, stirring is continued for 30min, and then 56.02g of MDI (set R value to be 1) is added to react and tackify at the temperature of 70-80 ℃. DMF can be properly added in batches for dilution in the tackifying process. And (3) after the reaction is finished, using methanol for end sealing, adding 15g of filler cellulose acetate and 4g of organic silicon softening agent after the end sealing is carried out for 1h, continuously stirring for 1h, and cooling the packed material. The viscosity of the obtained resin is 8-14 ten thousand (cps/DEG C), and the solid content is 30%.
II, conclusion
Taking 100g of the prepared dry-process fabric resin under the same condition, adding 3g of color chips and 100g of DMF, dispersing uniformly at a high speed, defoaming, coating the mixture on the surface of release paper, and drying in a drying oven at 110 ℃. Then coating PU adhesive on the leather, carrying out dry-process veneering, drying at 110 ℃, stripping from release paper, and then carrying out graining treatment on the leather to obtain the protein PU leather. The physical properties of the protein PU leather prepared by the 4 examples, such as surface smoothness, dust adhesion, softness, softening point and the like, are comprehensively evaluated, and the obtained experimental results are shown in Table 1.
TABLE 1 comparison of physical Properties of high temperature resistant protein PU dry top layer
From table 1, it can be seen that the high temperature resistant protein PU dry fabric prepared in example 4 has the best physical properties. The PU dry-process fabric obtained in the embodiment 4 has wider market prospect than other dry-process fabrics.
While embodiments of the invention have been disclosed above, it is not limited to the applications listed in the description and the embodiments, which are fully applicable in all kinds of fields of application of the invention, and further modifications may readily be effected by those skilled in the art, so that the invention is not limited to the specific details without departing from the general concept defined by the claims and the scope of equivalents.
Claims (8)
1. A preparation method of dry-process fabric resin for high-temperature-resistant protein PU leather is characterized by comprising the following steps:
1) putting polyester polyol, DMF, antioxidant BHT and phosphoric acid into a reaction bottle, uniformly stirring, adding isocyanate, and reacting at 70-80 ℃ for 1.5 h;
2) adding a chain extender into a reaction bottle, uniformly stirring, adding isocyanate, reacting and tackifying at 70-80 ℃ until the viscosity of the system reaches 8-14 ten thousand cps/DEG C;
3) and adding methanol for end capping after the tackifying reaction is finished, adding the filler and the auxiliary agent after the end capping is carried out for 1h, and then, continuously stirring for 1h and cooling the package material.
2. The method according to claim 1, wherein the polyester polyol is at least one selected from the group consisting of poly (methyl propylene adipate) glycol, poly (methyl propylene sebacate) glycol, and poly (methyl propylene sebacate) glycol.
3. The method according to claim 1, wherein the isocyanate in step 1) has an R value of 0.7.
4. The method according to claim 1, wherein the isocyanate in step 2) has an R value of 1.
5. The production method according to claim 1, wherein the chain extender is monoethanolamine.
6. The method of claim 1, wherein the filler is selected from the group consisting of SAN resin, PAN resin, ABS resin, cellulose acetate, and combinations thereof.
7. The method according to claim 1, wherein the auxiliary agent is a silicone softener.
8. A dry-process fabric resin for high-temperature-resistant protein PU leather prepared by the preparation method of any one of claims 1-7.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4048271A (en) * | 1972-10-02 | 1977-09-13 | Chemical Systems, Inc. | Dry process for forming polycarbonate membranes |
| EP1092738A2 (en) * | 1999-10-15 | 2001-04-18 | Solutia Austria GmbH | Waterdilutable binder for 'soft feel' lacquers |
| GB2540011A (en) * | 2015-04-30 | 2017-01-04 | Fujifilm Speciality Ink Systems Ltd | Method of printing |
| CN109467666A (en) * | 2018-09-30 | 2019-03-15 | 浙江禾欣科技有限公司 | A kind of preparation method of the polyurethane of surface slip |
| CN109736100A (en) * | 2019-01-22 | 2019-05-10 | 华大化学(安徽)有限公司 | A kind of high slipping dry-method chemical leather resin of middle hard and its preparation and application |
| CN109912761A (en) * | 2019-01-24 | 2019-06-21 | 扬州工业职业技术学院 | A kind of extra soft polyurethane wet process bass and preparation method thereof |
| CN110423333A (en) * | 2019-07-05 | 2019-11-08 | 浙江旭川树脂有限公司 | A kind of soft cryobranding color-changing polyurethane resin and its preparation method and application |
| CN110452350A (en) * | 2019-08-15 | 2019-11-15 | 台州禾欣高分子新材料有限公司 | A kind of preparation of leather polyurethane dry method surface layer resin and its application in vacuum pattern absorbing leather making process |
-
2020
- 2020-03-31 CN CN202010240550.6A patent/CN111363343B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4048271A (en) * | 1972-10-02 | 1977-09-13 | Chemical Systems, Inc. | Dry process for forming polycarbonate membranes |
| EP1092738A2 (en) * | 1999-10-15 | 2001-04-18 | Solutia Austria GmbH | Waterdilutable binder for 'soft feel' lacquers |
| GB2540011A (en) * | 2015-04-30 | 2017-01-04 | Fujifilm Speciality Ink Systems Ltd | Method of printing |
| CN109467666A (en) * | 2018-09-30 | 2019-03-15 | 浙江禾欣科技有限公司 | A kind of preparation method of the polyurethane of surface slip |
| CN109736100A (en) * | 2019-01-22 | 2019-05-10 | 华大化学(安徽)有限公司 | A kind of high slipping dry-method chemical leather resin of middle hard and its preparation and application |
| CN109912761A (en) * | 2019-01-24 | 2019-06-21 | 扬州工业职业技术学院 | A kind of extra soft polyurethane wet process bass and preparation method thereof |
| CN110423333A (en) * | 2019-07-05 | 2019-11-08 | 浙江旭川树脂有限公司 | A kind of soft cryobranding color-changing polyurethane resin and its preparation method and application |
| CN110452350A (en) * | 2019-08-15 | 2019-11-15 | 台州禾欣高分子新材料有限公司 | A kind of preparation of leather polyurethane dry method surface layer resin and its application in vacuum pattern absorbing leather making process |
Non-Patent Citations (3)
| Title |
|---|
| 孔萍等: "《塑料材料》", 31 July 2017, 广东高等教育出版社 * |
| 王霞等: "《现代建筑涂料：树脂合成与配方设计》", 30 September 2005 * |
| 赵辉等: ""脲基的引入对聚氨酯弹性体性能的影响"", 《平顶山工学院学报》 * |
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