CN113501929A - Flame-retardant wear-resistant polyurethane resin for leather - Google Patents

Flame-retardant wear-resistant polyurethane resin for leather Download PDF

Info

Publication number
CN113501929A
CN113501929A CN202110851472.8A CN202110851472A CN113501929A CN 113501929 A CN113501929 A CN 113501929A CN 202110851472 A CN202110851472 A CN 202110851472A CN 113501929 A CN113501929 A CN 113501929A
Authority
CN
China
Prior art keywords
flame
polyurethane resin
parts
leather
resistant polyurethane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202110851472.8A
Other languages
Chinese (zh)
Inventor
倪俨杰
韩驭章
林佳琪
王元有
周龙生
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Yangzhou Polytechnic Institute
Original Assignee
Yangzhou Polytechnic Institute
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Yangzhou Polytechnic Institute filed Critical Yangzhou Polytechnic Institute
Priority to CN202110851472.8A priority Critical patent/CN113501929A/en
Publication of CN113501929A publication Critical patent/CN113501929A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • 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
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
    • C08G18/3889—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
    • 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
    • C08G18/28—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
    • C08G18/61—Polysiloxanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)

Abstract

The scheme relates to a flame-retardant wear-resistant polyurethane resin for leather, which is prepared from the following raw materials in parts by weight: 200-300 parts of polyester polyol; 100-140 parts of isocyanate; 35-50 parts of a chain extender; 1-4 parts of trifunctional organosilicon; 0.1-0.2 part of antioxidant; 900-1100 parts of DMF. The chain extender is nitrogenous phosphate dihydric alcohol and is prepared by the following method: putting phosphite, an aldehyde compound and a nitrogen-containing compound into a reaction kettle, reacting at 75-90 ℃ to obtain nitrogen-containing phosphate dihydric alcohol and water, and removing the water to obtain the product. According to the invention, the nitrogenous phosphate ester polyol is used as a chain extender, and the polyester polyol with a specific structure and the trifunctional organosilicon with a proper amount are matched, so that the flame retardant effect of the polyurethane resin is effectively improved, and the color development performance of the PU resin is promoted; the friction resistance of the leather is effectively improved when the synthetic leather is prepared.

Description

Flame-retardant wear-resistant polyurethane resin for leather
Technical Field
The invention belongs to the technical field of polyurethane synthesis, and particularly relates to flame-retardant wear-resistant polyurethane resin for leather.
Background
The dry-process polyurethane resin (PU) mainly comprises a chain extender, polyol, isocyanate and a solvent. Wherein the types and the compositions of the chain extender and the polyhydric alcohol have important influence on the flame retardant, the wear resistance and the color development performance of the dry-process PU. Benzene rings, P, Br, Cl, N and the like contained in PU are derived from a chain extender or polyhydric alcohol, and the abundant elements exist in the polyhydric alcohol or the chain extender in any form, and the proportion of the elements in PU molecular chains can all have important influence on the performance of the finally prepared synthetic leather. For example, benzene ring burn insufficiently and cover the surface with carbon deposits, which prevents the resin from further burning by contacting with air. The P-containing PU resin generates polyphosphoric acid when being burnt, and the PU resin is catalyzed to generate a carbon-containing layer (as a protective layer) under high temperature condition to prevent the flame retardant effect. The PU resin containing Cl and Br can generate chain chemical reaction of hydrogen ions during combustion, and the flame is interrupted to achieve the purpose of extinguishing the fire, so the PU resin is generally called as an automatic fire extinguishing material.
In the development of flame-retardant PU resins, researchers have generally filled PU resins with additive flame retardants or reactive flame retardants, the additive flame retardants being mainly inorganic flame retardants (e.g., magnesium hydroxide, aluminum hydroxide, expandable graphite, etc.). The reactive flame retardant is prepared by grafting a flame retardant element into a PU molecular chain through a chemical reaction. Although the addition of the flame retardant is helpful for improving the flame retardant performance of the synthetic leather, the compatibility of the filler and the auxiliary agent with the polyurethane resin is not good, the leveling and color spreading of the synthetic leather are easy to deteriorate, and even the surface of the synthetic leather is sometimes fogged due to precipitation. In addition, carbon black with relatively high cost performance is generally adopted when PU resin is dyed by a dry method, but the adhesion of the carbon black on the surface of PU is a great problem. For example, PU resin synthesized by PEA, dry coating made by using carbon black as dye, has whitish surface, and synthetic leather made by PU resin synthesized by PBA is black. The appearance of fogging (blushing) on the surface of the dry coating may be caused by the formation of flocculation of carbon black on the surface of the PU resin, and such a phenomenon is generally referred to as "color migration".
Therefore, it is necessary to develop a dry-process polyurethane resin with flame retardancy, wear resistance and high color development.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to synthesize the PU synthetic leather with flame retardance, wear resistance and high color development by synthesizing nitrogen-containing phosphate ester polyol as a chain extender and grafting the nitrogen-containing phosphate ester polyol into polyurethane resin through reactive organic silicon.
In order to achieve the purpose, the invention provides the following technical scheme:
the flame-retardant wear-resistant polyurethane resin for leather is prepared from the following raw materials in parts by weight:
Figure BDA0003182464270000021
the chain extender is nitrogenous phosphate dihydric alcohol and is prepared by the following method: putting phosphite, an aldehyde compound and a nitrogen-containing compound into a reaction kettle, reacting at 75-90 ℃ to obtain nitrogen-containing phosphate dihydric alcohol and water, and removing the water to obtain the product.
Preferably, the phosphite is selected from one or more of dimethyl phosphite, cyclic phosphates, and phenyl phosphates.
Preferably, the aldehyde is one or more of formaldehyde, acetaldehyde and propionaldehyde.
Preferably, the nitrogen-containing compound is one or more of monoethanolamine, diethanolamine and triethanolamine.
Preferably, the molar ratio of phosphite, hydroformylation compound and nitrogen-containing compound is 1:1: 1.
Preferably, the polyester polyol is selected from one or more of polyethylene glycol butanediol adipate diol, polybutylene glycol hexanediol adipate diol, and polytrimethylene glycol butanediol adipate diol.
Preferably, the trifunctional organic silicon is one or more of polyether modified organic silicon, modified polysiloxane, polyester modified organic silicon and modified silicone.
The PU leather is often subjected to friction action in the use process of some special occasions, and the traditional method for improving the wear resistance of the PU leather is to add various organic silicon auxiliaries into PU resin, reduce the friction coefficient of the PU leather and improve the wear resistance of the PU leather through the lubricating action of organic silicon. However, according to the similar compatibility principle, the compatibility of the organic silicon and the polyurethane resin is not very good, and sometimes, the risk of precipitation is also existed, namely, the synthetic leather surface is easy to be fogged. The present case is through adding in a small amount of trifunctional organic silicon grafting advances the PU resin for the PU resin can form the cross-linking network structure of certain degree, and the rigidity of resin can not only be strengthened to the structure of cross-linking, promotes its antifriction performance, and organosilicon itself plays certain lubrication action in addition, can both promote the antifriction power of final synthetic leather in the follow two aspects. However, the proportion of the trifunctional organosilicon in the whole raw material components is important, if the proportion is too large, the crosslinking degree of the PU resin is easily too large, the foaming performance of the PU resin is affected, and if the proportion is too small, the trifunctional organosilicon does not play a wear-resisting role.
The polyol used by the PU leather resin is mainly polyester polyol, and the physical property difference of different types of polyester polyol is large, thereby having important influence on the wear resistance and color development performance of the PU resin. The present case discovers in the research, through adopting dibasic acid and the polyester polyol that different dihydric alcohols polycondensation prepared, arranges irregularly between its molecular chain, has reduced the crystallization property of whole PU resin, can be with firm absorption in the molecular chain of polyurethane resin of dye molecule when being applied to polyurethane resin synthetic leather to help the promotion of synthetic leather exhibition of color ability.
Compared with the prior art, the invention has the beneficial effects that:
1. the nitrogen-containing phosphate ester polyol with high flame retardant property prepared by the Mannich reaction is used as a chain extender, so that the flame retardant effect of the polyurethane resin is effectively improved, the nitrogen energy in the nitrogen-containing phosphate ester polyol and the oxygen-containing functional groups in the color chip (carbon black) form firm hydrogen bonds, the color chip molecules are firmly adsorbed in the molecular chain of the polyurethane resin, and the improvement of the color development property of the PU resin is facilitated.
2. According to the invention, different dihydric alcohols are selected as the polyester polyol of the main raw material, and different components enable the arrangement of polyol molecular chains to be irregular, so that the crystallization performance of the whole PU resin is reduced, the interpenetration of color chip micromolecules is facilitated, and the color development of the resin is improved.
3. By adding a proper amount of trifunctional organosilicon and grafting the trifunctional organosilicon into the PU resin, the rigidity of the PU resin is improved, and the friction resistance of the leather is effectively improved when the synthetic leather is prepared.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but 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.
The flame-retardant wear-resistant polyurethane resin for leather is prepared from the following raw materials in parts by weight: 200-300 parts of polyester polyol; 100-140 parts of isocyanate; 35-50 parts of nitrogenous phosphate dihydric alcohol; 1-4 parts of trifunctional organosilicon; 0.1-0.2 part of antioxidant; 900-1100 parts of N, N-Dimethylformamide (DMF).
The isocyanate and the antioxidant in the raw materials are common materials in polyurethane resin, the scheme is not limited, and the isocyanate and the antioxidant and the materials can be purchased from the market except for special description.
Example 1:
the nitrogen-containing phosphate diol of this example was prepared as follows: putting 1mol of dimethyl phosphite, 1mol of formaldehyde and 1mol of monoethanolamine into a reaction kettle, reacting at 75-90 ℃, and removing water to obtain the chain extender A, wherein the reaction product is nitrogenous phosphate dihydric alcohol and water.
The raw materials for preparing the polyurethane resin in this example were: 200 parts of poly (ethylene glycol adipate) butanediol glycol, 100 parts of isophorone isocyanate, 40 parts of chain extender A, 1 part of trifunctional polyether modified organic silicon, 10100.1 parts of antioxidant and 1000 parts of solvent DMF.
The polyurethane resin was prepared as follows: putting the poly (ethylene glycol adipate) butanediol glycol, the antioxidant, the chain extender A, the trifunctional group polyether modified organic silicon and a certain amount of solvent into a reaction kettle, and fully stirring for 30 min. Then adding isocyanate, keeping the R value at 1, heating to 70-75 ℃ to react and tackify the mixture, and supplementing a small amount of isocyanate to promote the reaction in the tackification process; and simultaneously adding the rest solvent, adding a terminator methanol when the viscosity of the resin reaches 20-24 million (cps), continuously stirring for 1h, cooling and packaging. The solid content of the final polyurethane resin A is controlled to be 30 percent.
The flame-retardant wear-resistant and high-color-spreading polyurethane synthetic leather is prepared by the following steps: taking 100g of the synthetic polyurethane resin A in a bottle, adding 5g of carbon black and 100g of solvent DMF into the bottle, uniformly dispersing at a high speed at a stirring speed of 4000r/min, and then standing for defoaming; and coating the surface of release paper with the polyurethane dry-process primer, placing the release paper in an oven for complete drying, coating the polyurethane dry-process primer on the surface of the release paper, then attaching a microfiber bass layer, placing the release paper in the oven for drying, and then stripping the release paper to obtain the synthetic leather.
Example 2:
the nitrogen-containing phosphate diol of this example was prepared as follows: putting 1mol of cyclic phosphate, 1mol of acetaldehyde and 1mol of diethanolamine into a reaction kettle, reacting at 75-90 ℃, and removing water to obtain a chain extender B, wherein the reaction product is a nitrogenous phosphate dihydric alcohol and water.
The raw materials for preparing the polyurethane resin in this example were: 200 parts of poly-hexamethylene glycol adipate diol, 100 parts of isophorone isocyanate, 40 parts of chain extender B, 1 part of trifunctional polyester modified organic silicon, 10100.1 parts of antioxidant and 1000 parts of solvent DMF.
The procedure for preparing the polyurethane resin of this example was the same as in example 1.
The preparation process of the flame-retardant, wear-resistant and high-color-developability polyurethane synthetic leather of the embodiment is the same as that of the embodiment 1.
Example 3:
the nitrogen-containing phosphate diol of this example was prepared as follows: putting 1mol of phenyl phosphate, 1mol of propionaldehyde and 1mol of triethanolamine into a reaction kettle, reacting at 75-90 ℃, and removing water to obtain the chain extender C.
The raw materials for preparing the polyurethane resin in this example were: 200 parts of poly (methyl propylene glycol adipate) butanediol glycol, 100 parts of isophorone isocyanate, 40 parts of chain extender C, 1 part of trifunctional polyether modified organic silicon, 10100.1 parts of antioxidant and 1000 parts of solvent DMF.
The procedure for preparing the polyurethane resin of this example was the same as in example 1.
The preparation process of the flame-retardant, wear-resistant and high-color-developability polyurethane synthetic leather of the embodiment is the same as that of the embodiment 1.
Example 4:
the raw materials for preparing the polyurethane resin in this example were: 200 parts of poly (methyl propylene glycol adipate) butanediol glycol, 100 parts of isophorone isocyanate, 10 parts of chain extender C, 0.5 part of trifunctional modified silicone, 10100.1 parts of antioxidant and 1000 parts of solvent DMF.
The procedure for preparing the polyurethane resin of this example was the same as in example 1.
The preparation process of the flame-retardant, wear-resistant and high-color-developability polyurethane synthetic leather of the embodiment is the same as that of the embodiment 1.
Example 5:
the raw materials for preparing the polyurethane resin in this example were: 200 parts of poly (methyl propylene glycol adipate) butanediol glycol, 100 parts of isophorone isocyanate, 10 parts of chain extender C, 1 part of trifunctional polyester modified organic silicon, 10100.1 parts of antioxidant and 1000 parts of solvent DMF.
The procedure for preparing the polyurethane resin of this example was the same as in example 1.
The preparation process of the flame-retardant, wear-resistant and high-color-developability polyurethane synthetic leather of the embodiment is the same as that of the embodiment 1.
Comparative example 1
It differs from example 1 in that the chain extender a is replaced by ethylene glycol.
Comparative example 2
It differs from example 1 in that the chain extender a is replaced by monoethanolamine.
Comparative example 3
It differs from example 1 in that the polyester polyol is chosen to be a mixture of polyethylene glycol adipate and polybutylene adipate.
Wear resistance: a Taber resistant mill is adopted, an H-shaped rubber grinding wheel is used, a 500g weight is loaded, and the abrasion resistance is very good if the synthetic leather is completely damaged after the test according to GB/T1768-79. If the surface of the synthetic leather is damaged at 500 revolutions, the wear resistance is general; when the rotation number is less than 500, the wear resistance is inferior if the surface of the synthetic leather is damaged.
Flame retardancy: the combustion performance test standard of the FMVSS-302 internal material is that prepared PU leather is cut into strips and marked with scales, and then the strips are ignited by fire to test the combustion rate. The burning speed is 0mm/min, which is a superior grade; the burning speed is less than 50mm/min, the requirement of burning speed is met, and the product is good; the burning speed is 50-100 mm/min, the burning speed requirement is met, and the method is general; the burning speed is more than 100mm/min, and the product is not qualified.
Color development performance: the darker the color, the better the color development performance, judged by the color of the final synthetic leather.
The synthetic leather performance indexes of examples 1-5 and comparative examples 1-3 were tested, and the results are shown in table 1.
TABLE 1
Name of sample Flame-retardant Wear-resistant Color spreading
Example 1 Superior food Superior food Superior food
Example 2 Superior food Superior food In general
Example 3 Good wine Superior food In general
Example 4 In general Bad quality Superior food
Example 5 In general Bad quality Superior food
Comparative example 1 Fail to be qualified In general Bad quality
Comparative example 2 In general In general Bad quality
Comparative example 3 Fail to be qualified In general In general
Table 1 shows that the synthetic leather prepared in the example 1 has excellent performances, and the synthetic leather with flame retardance, wear resistance and good color development performance is successfully prepared by the scheme. By comparing examples 4 and 5, it can be found that the content of the trifunctional group organosilicon has an important influence effect in the whole preparation of the polyurethane resin, and more or less of the trifunctional group organosilicon is not beneficial to the wear resistance of the synthetic leather; the comparative examples 1 to 3 show that the polyester polyol selected by the scheme is beneficial to reducing the crystallization property of the whole PU resin and improving the color development of the resin, thereby improving the color development of the synthetic leather.
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 (7)

1. The flame-retardant wear-resistant polyurethane resin for leather is characterized by being prepared from the following raw materials in parts by weight:
Figure FDA0003182464260000011
the chain extender is nitrogenous phosphate dihydric alcohol and is prepared by the following method: putting phosphite, an aldehyde compound and a nitrogen-containing compound into a reaction kettle, reacting at 75-90 ℃ to obtain nitrogen-containing phosphate dihydric alcohol and water, and removing the water to obtain the product.
2. The flame-retardant abrasion-resistant polyurethane resin for leather according to claim 1, wherein said phosphite is one or more selected from the group consisting of dimethyl phosphite, cyclic phosphates and phenyl phosphates.
3. The flame-retardant abrasion-resistant polyurethane resin for leather according to claim 1, wherein the aldehyde is one or more of formaldehyde, acetaldehyde and propionaldehyde.
4. The flame-retardant abrasion-resistant polyurethane resin for leather according to claim 1, wherein said nitrogen-containing compound is one or more of monoethanolamine, diethanolamine and triethanolamine.
5. The flame-retardant abrasion-resistant polyurethane resin for leather according to claim 1, wherein the molar ratio of the phosphite, the aldehyde and the nitrogen-containing compound is 1:1: 1.
6. The flame-retardant abrasion-resistant polyurethane resin for leather according to claim 1, wherein said polyester polyol is one or more selected from the group consisting of polyethylene glycol butanediol adipate diol, polybutylene glycol hexanediol adipate diol, and polytrimethylene glycol butanediol adipate diol.
7. The flame-retardant abrasion-resistant polyurethane resin for leather according to claim 1, wherein the trifunctional silicone is one or more of polyether-modified silicone, modified polysiloxane, polyester-modified silicone and modified silicone.
CN202110851472.8A 2021-07-27 2021-07-27 Flame-retardant wear-resistant polyurethane resin for leather Pending CN113501929A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110851472.8A CN113501929A (en) 2021-07-27 2021-07-27 Flame-retardant wear-resistant polyurethane resin for leather

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110851472.8A CN113501929A (en) 2021-07-27 2021-07-27 Flame-retardant wear-resistant polyurethane resin for leather

Publications (1)

Publication Number Publication Date
CN113501929A true CN113501929A (en) 2021-10-15

Family

ID=78014176

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110851472.8A Pending CN113501929A (en) 2021-07-27 2021-07-27 Flame-retardant wear-resistant polyurethane resin for leather

Country Status (1)

Country Link
CN (1) CN113501929A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114196314A (en) * 2021-12-24 2022-03-18 广东粤港澳大湾区黄埔材料研究院 Flame-retardant wear-resistant coating and application thereof in preparation of flame-retardant scratch-resistant coating

Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102174167A (en) * 2011-02-17 2011-09-07 陈华 Organic silicon modified polyurethane resin for synthetic leather and preparation method thereof
CN102276645A (en) * 2011-05-18 2011-12-14 烟台万华聚氨酯股份有限公司 Preparation method of diethyl N,N-bis(2- hydroxyethyl) aminomethylphosphonate
CN102604026A (en) * 2011-02-17 2012-07-25 浙江深蓝轻纺科技有限公司 Organic silicon-modified polyurethane resin for synthetic leather and preparation method thereof
CN103554426A (en) * 2013-10-29 2014-02-05 上海汇得化工有限公司 Brand discoloration wet-process polyurethane resin with good hydrolysis resistance
CN103965247A (en) * 2014-05-23 2014-08-06 厦门大学 Phosphor-containing nitrogen-containing structural type flame retardant polyhydric alcohol as well as preparation method and application thereof
CN104086737A (en) * 2014-07-01 2014-10-08 中国林业科学研究院林产化学工业研究所 Method for preparing flame-retardant toughening polyurethane semi-prepolymer for phenolic foam
CN104448217A (en) * 2014-12-12 2015-03-25 北京天山新材料技术有限公司 Highly-antistatic flame-retardant rapidly-cured conveying belt mending agent and preparation process thereof
CN104513273A (en) * 2013-09-29 2015-04-15 青岛市首胜实业有限公司 Preparation method for organic phosphorus flame retardant N, N dihydroxyethyl aminomethyl diethyl phosphonate
CN104592297A (en) * 2015-01-28 2015-05-06 中国科学技术大学 Flame-retardant glycol containing phenyl phosphate-based symmetrical structure and preparation method thereof
CN106519177A (en) * 2015-09-11 2017-03-22 安徽安利材料科技股份有限公司 Method for manufacturing embossed solvent-free polyurethane synthetic leather
CN106750084A (en) * 2016-11-25 2017-05-31 上海华峰超纤材料股份有限公司 High solids content two-liquid type bonding layer polyurethane resin and preparation method thereof
CN107602804A (en) * 2017-09-22 2018-01-19 江苏多森化工有限公司 A kind of preparation method of formula of extinguishing waterborn polyurethane and preparation method thereof and extinguishing waterborn polyurethane bass
CN108864184A (en) * 2018-06-09 2018-11-23 河北晟凯新材料科技有限公司 A kind of synthesis N, N- bis-（2- ethoxy）The method of aminomethyl phosphonic acid diethylester
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

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102604026A (en) * 2011-02-17 2012-07-25 浙江深蓝轻纺科技有限公司 Organic silicon-modified polyurethane resin for synthetic leather and preparation method thereof
CN102174167A (en) * 2011-02-17 2011-09-07 陈华 Organic silicon modified polyurethane resin for synthetic leather and preparation method thereof
CN102276645A (en) * 2011-05-18 2011-12-14 烟台万华聚氨酯股份有限公司 Preparation method of diethyl N,N-bis(2- hydroxyethyl) aminomethylphosphonate
CN104513273A (en) * 2013-09-29 2015-04-15 青岛市首胜实业有限公司 Preparation method for organic phosphorus flame retardant N, N dihydroxyethyl aminomethyl diethyl phosphonate
CN103554426A (en) * 2013-10-29 2014-02-05 上海汇得化工有限公司 Brand discoloration wet-process polyurethane resin with good hydrolysis resistance
CN103965247A (en) * 2014-05-23 2014-08-06 厦门大学 Phosphor-containing nitrogen-containing structural type flame retardant polyhydric alcohol as well as preparation method and application thereof
CN104086737A (en) * 2014-07-01 2014-10-08 中国林业科学研究院林产化学工业研究所 Method for preparing flame-retardant toughening polyurethane semi-prepolymer for phenolic foam
CN104448217A (en) * 2014-12-12 2015-03-25 北京天山新材料技术有限公司 Highly-antistatic flame-retardant rapidly-cured conveying belt mending agent and preparation process thereof
CN104592297A (en) * 2015-01-28 2015-05-06 中国科学技术大学 Flame-retardant glycol containing phenyl phosphate-based symmetrical structure and preparation method thereof
CN106519177A (en) * 2015-09-11 2017-03-22 安徽安利材料科技股份有限公司 Method for manufacturing embossed solvent-free polyurethane synthetic leather
CN106750084A (en) * 2016-11-25 2017-05-31 上海华峰超纤材料股份有限公司 High solids content two-liquid type bonding layer polyurethane resin and preparation method thereof
CN107602804A (en) * 2017-09-22 2018-01-19 江苏多森化工有限公司 A kind of preparation method of formula of extinguishing waterborn polyurethane and preparation method thereof and extinguishing waterborn polyurethane bass
CN108864184A (en) * 2018-06-09 2018-11-23 河北晟凯新材料科技有限公司 A kind of synthesis N, N- bis-（2- ethoxy）The method of aminomethyl phosphonic acid diethylester
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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114196314A (en) * 2021-12-24 2022-03-18 广东粤港澳大湾区黄埔材料研究院 Flame-retardant wear-resistant coating and application thereof in preparation of flame-retardant scratch-resistant coating

Similar Documents

Publication Publication Date Title
JP2618844B2 (en) Spreading paste containing polyurethane and / or polyurethane urea and method for producing a water vapor permeable coating
US20030212192A1 (en) Non-yellowing polyester coating composition
CN104530371A (en) Halogen-free persistent form inflaming retarding water-borne polyurethane and preparation method thereof
JPH02187477A (en) Coating material containing pur dispersion and solvent, and its use for preparation of steam-permeable pur coating
WO2015176623A1 (en) Halogen-free phosphorus-containing flame-retardant rigid polyurethane foam plastic and preparation method therefor
CN111269390B (en) Polyurethane resin for synthetic leather surface layer and preparation method thereof
CN109705719A (en) A kind of extinguishing waterborn polyurethane coating
CN108129635B (en) Hydrophobic flame-retardant water-based curing agent and preparation method thereof
CN113501929A (en) Flame-retardant wear-resistant polyurethane resin for leather
CN113336915A (en) Wear-resistant polyurethane for solid tire and preparation method thereof
CN108707412B (en) Weak-solvent high-brightness resin and preparation method thereof
CN108252104B (en) Preparation method of textile smoothing agent
JPS6324009B2 (en)
TWI394766B (en) Phosphorous-containing waterborne polyurethane
CN112680096A (en) Preparation method of surface treating agent for synthetic leather
CN107266655B (en) Phosphorus-nitrogen synergistic intumescent self-flame-retardant waterborne polyurethane and preparation method thereof
CN100549091C (en) Composition epoxy resin and epoxy-polysiloxane coating composition
CN112280450A (en) PVC artificial leather water-based color-changing treatment agent and preparation method thereof
CN111304931A (en) Wear-resistant flame-retardant floor leather for vehicles and preparation method thereof
CN110863365A (en) Lightweight flame-retardant organic silicon synthetic leather and preparation method thereof
CN114379175A (en) Water-based environment-friendly high-flame-retardant solvent-free embossed grain-absorbing synthetic leather and preparation method thereof
CN114507989A (en) Anti-whitening PU synthetic leather and preparation method thereof
CN111607218A (en) Polyurethane flame-retardant film, preparation method and application thereof
CN109593173B (en) Silicon-based thermoplastic vulcanized rubber with flame retardance and synthetic method thereof
CN112375203A (en) Sericin modified waterborne polyurethane waterproof moisture-permeable coating and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20211015