CN110183609A - A kind of solvent-free polyurethane resin and its application - Google Patents
A kind of solvent-free polyurethane resin and its application Download PDFInfo
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- CN110183609A CN110183609A CN201910326703.6A CN201910326703A CN110183609A CN 110183609 A CN110183609 A CN 110183609A CN 201910326703 A CN201910326703 A CN 201910326703A CN 110183609 A CN110183609 A CN 110183609A
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- 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
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- 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
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4676—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing sulfur
-
- 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
- C08G18/48—Polyethers
-
- 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
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6611—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
-
- 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
-
- 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
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1664—Releasability
-
- 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
- D06N2209/00—Properties of the materials
- D06N2209/16—Properties of the materials having other properties
- D06N2209/1692—Weather resistance
-
- 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
- D06N2211/00—Specially adapted uses
- D06N2211/12—Decorative or sun protection articles
- D06N2211/28—Artificial leather
Abstract
A kind of solvent-free polyurethane resin, it is mixed by component A and component B, wherein, in the component A, including 30-70 mass parts polyether polyol, 30-70 mass parts sulfonate polyester polyol, 5-15 mass parts small molecule chain extender, 0-5 mass parts crosslinking agent and 0.1-1.5 mass parts water, 0.025-0.05 mass parts of catalyst, 0.1-5 mass parts sulfonate type chain extender, 0.1-2 mass parts foam stabiliser；In the B component, including 10-30 mass parts polyether polyol, 10-30 mass parts sulfonate polyester polyol and 40-60 mass parts isocyanates；The solvent-free polyurethane resin is applied to sulfonic acid type water-base resin, greatly improves initial bonding strength and hydrolysis conservation rate.
Description
Technical field
The invention belongs to material industry fields, and in particular to a kind of solvent-free polyurethane resin and its application.
Background technique
In recent years, the development of Waterborne synthetic leather and uninanned platform leather is advanced by leaps and bounds, and in technical research and production technology
It is upper to obtain a series of major progresses, new opportunity is brought for the transition and upgrade of synthetic leather industry.Uninanned platform removes from office product at present
There are still the problem of be that water-base resin surface layer and no-solvent polyurethane foaming layer adhesion strength are poor, gained synthetic leather product removing
Intensity is lower, can not be applied in the product more demanding to peel strength.
The application in view of the defects existing in the prior art, improves the ingredient of solvent-free polyurethane resin, by product
Applied to sulfonic acid type water-base resin, achieve the purpose that improve peel strength.
Summary of the invention
The present invention is intended to provide a kind of solvent-free polyurethane resin, which is free of any organic solvent, energy consumption
Low, high production efficiency, and it is high with the peel strength of the aqueous covercoat of sulfonic acid type water-base resin.
To solve the above problems, the present invention is achieved by the following technical solutions:
A kind of solvent-free polyurethane resin is mixed by component A and component B, wherein in the component A, including 30-
70 mass parts polyether polyol, 30-70 mass parts sulfonate polyester polyol, 5-15 mass parts small molecule chain extender, 0-5 mass
Part crosslinking agent and 0.1-1.5 mass parts water, 0.025-0.05 mass parts of catalyst, 0.1-5 mass parts sulfonate type chain extender,
0.1-2 mass parts foam stabiliser；In the B component, including 10-30 mass parts polyether polyol, 10-30 mass parts sulfonate
The pure and mild 40-60 mass parts isocyanates of polyester polyols.
Optionally, the sulfonate type chain extender is Diaminoalkyl sulfonate or unsaturated dihydric alcohol and sodium hydrogensulfite
Addition product.
Optionally, the polypropylene oxide glycol or molecular weight 5000 that the polyether polyol is molecular weight 1000-2000~
One of 6000 high activity polyether triol.
Optionally, the molecular weight of the sulfonate polyester polyol is 1000-2000.The sulfonate polyester polyol by
It is sulfonated obtained that following components passes through dehydrating polycondensation in parts by weight: 40-80 parts of adipic acid, 30-60 parts of small molecule dihydric alcohol, and titanium
Sour 0.01-0.06 parts of four butyl ester catalyst is made polyester polyol through sulfonated and obtains sulfonate polyester polyol.
Optionally, the small molecule chain extender is diethanol amine, ethylenediamine, ethylene glycol, 1,2-PD, 1,3- the third two
Alcohol, 1,4-butanediol, 1,5-PD, neopentyl glycol, diglycol, dipropylene glycol, 3- methyl-1,5- penta 2
One or more of bis- (2- ethoxy) ethers of alcohol, 1,6-HD, 1,4 cyclohexane dimethanol quinhydrones.
Optionally, the crosslinking agent is one or more of glycerine, trimethylolpropane, triethanolamine.
Optionally, the catalyst is BiCAT 8106, BiCAT 8108, BiCAT 8124, BiCAT 3228, Borchi
Kat22, Borchi Kat 24, BiCAT 4130, BiCAT 4232, MB20 and above-mentioned organometallic catalysts phenolate,
The phenolate of formates, hydrochloride, DBU, triethylene triamine, A1 and above-mentioned amines catalyst, formates, in ethylhexanoate salt
One or more of.
Optionally, the foam stabiliser is organic silicon modified by polyether surfactant.
Another goal of the invention of the invention is to provide a kind of application of above-mentioned solvent-free polyurethane resin, described solvent-free
Polyurethane resin is applied to sulfonic acid type water-base resin.
In the present invention, solvent-free polyurethane resin prepared by the present invention is applied on sulfonic acid type water-base resin, is substantially mentioned
Initial bonding strength and hydrolysis conservation rate have been risen, the production operation tolerance of aqueous/uninanned platform leather is enhanced；Due to water
Property/uninanned platform leather be free of any organic solvent, make to have many advantages, such as environmentally protective, soft, plentiful, physical property
Reach room temperature and deflect 100,000 times and do not crack, deflect for cold-resistant -10 DEG C × 80,000 times and not crack, initial bonding strength be 80N/3cm with
On, permanent peel strength is 100N/3cm or more, and 5 weeks peel strength retention rates can under the conditions of 70 DEG C × 95% humidity constant temperature and humidity
Up to 85% or more.
Specific embodiment
Below by several specific embodiments, the present invention is further illustrated, but it is to be noted that of the invention
Specific material proportion, process conditions and result etc. described in embodiment are merely to illustrate the present invention, can not be limited with this
Protection scope of the present invention processed, equivalent change or modification made by all Spirit Essences according to the present invention, should all cover
In protection scope of the present invention.
(1) component A is prepared:
Polyether polyol, sulfonate polyester polyol are dehydrated 3- under the conditions of 90-110 DEG C, -0.08MPa~-0.1MPa
5h is spare；Dewatered polyether polyol, sulfonate polyester polyol are added in reaction kettle, adjusts and constant temperature is in 40-60
DEG C, chain extender, crosslinking agent, water, catalyst, foam stabiliser, sulfonate type chain extender are sequentially added, 4-6h is stirred,
Obtain component A；
(2) component B is prepared:
Isocyanates is put into reaction kettle and is uniformly mixed, dewatered polyether polyol, sulfonic acid is then added
Salt polyester polyol, is warming up to 70-80 DEG C, is stirred to react 4-6h, obtains component B；
(3) preparation of uninanned platform leather:
The KT3010 sulfonic acid type water-base resin that the aqueous Ke Tian Materials Co., Ltd in Hefei is coated in release paper, by 130
It DEG C forms within dry 2 minutes, obtains surface layer；Component A and component B is sufficiently mixed in low-pressure casting machine according to a certain mass ratio,
Solvent-free polyurethane resin, and be poured be coated on aqueous covercoat on, subsequently into 110 DEG C baking oven pre-reaction 60 seconds, pre-reaction
After be bonded base fabric, then the reaction was continued 7 minutes in 100-150 DEG C, forms its crosslinking curing；It will be release after curing molding
Paper removing, and wind, high removing uninanned platform leather is obtained, is tested peel strength (as initial bonding strength), nothing obtained
Solvent synthetic leather again through 70 DEG C, test peel strength (as permanent peel strength), 5 weeks peel strength retention rates by post curing for 24 hours
(70 DEG C × 95% humidity), deflects for room temperature 23 DEG C × 100,000 times, deflects for cold-resistant -10 DEG C × 80,000 times.
The chemicals used in embodiment and comparative example is as follows:
Polyether polyol: the DP-4000 purchased from the production of Kunshan national capital Chemical Co., Ltd..
Sulfonate polyester polyol: the BY3301 purchased from one hundred source Chemical Co., Ltd. of Beijing.
Small molecule chain extender: commercially available 1,4- butanediol product.
Crosslinking agent: commercially available trimethylolpropane product.
Catalyst: 8124 organic bismuth catalyst of BiCAT purchased from the leading chemical company production in the U.S..
Foam stabiliser: the DC-193 organic silicon modified by polyether foam stabiliser purchased from the production of air chemical company, the U.S..
Isocyanates: the pure diphenylmethylene diisocyanate of MDI-100 purchased from the production of Yantai Wanhua company.
Dihydromethyl propionic acid: commercial product.
Symbol description
DP-4000 polyether polyol
BY3301 sulfonate polyester polyol
One kind of 8124 organic bismuth catalyst of BiCAT
One kind of DC-193 organic silicon modified by polyether foam stabiliser
A95 sulfonate type chain extender
The pure diphenylmethylene diisocyanate of MDI-100.
Embodiment 1
(1) component A is prepared:
It is spare that DP-4000, BY3301 are dehydrated to 3-5h under the conditions of 90-110 DEG C, -0.08MPa~-0.1MPa；It will dehydration
70 parts of 30 parts of DP-4000, BY3301 afterwards is added in reaction kettle, adjusts and constant temperature is at 40-60 DEG C, sequentially add Isosorbide-5-Nitrae-
5 parts of butanediol, 5 parts of trimethylolpropane, 0.1 part of water, 8,124 0.025 parts of BiCAT, 0.1 part of DC-193, sulfonate type expand
0.1 part of chain agent A95 is stirred 4-6h, obtains component A；
(2) component B is prepared:
It in 40 parts of investment reaction kettles of MDI-100 and will be uniformly mixed, dewatered DP-4000 10 be then added
Part, 30 parts of BY3301, are warming up to 70-80 DEG C, are stirred to react 4-6h, obtain component B；
(3) preparation of uninanned platform leather:
The KT3010 sulfonic acid type water-base resin of the aqueous Ke Tian Materials Co., Ltd in Hefei is coated in release paper, 130 DEG C dry
It forms within dry 2 minutes, obtains surface layer；Component A and component B is sufficiently mixed in low-pressure casting machine by 100/115 mass ratio, is obtained
Solvent-free polyurethane resin, and be poured be coated on aqueous covercoat on, subsequently into 110 DEG C baking oven pre-reaction 60 seconds, pre-reaction knot
Base fabric is bonded after beam, then the reaction was continued 7 minutes in 100-150 DEG C, forms its crosslinking curing；By release paper after curing molding
Removing, and wind, high removing uninanned platform leather is obtained, test peel strength (as initial bonding strength) is 32N/3cm, system
Uninanned platform leather again through 70 DEG C, post curing for 24 hours, test peel strength (as permanent peel strength) is 43N/3cm, 5
All peel strength retention rates (70 DEG C × 95% humidity) are 86%, deflect for room temperature 23 DEG C × 100,000 times not crack, resist cold -10 DEG C
It deflects not crack for × 8 ten thousand times.
Embodiment 2
(1) component A is prepared:
It is spare that DP-4000, BY3301 are dehydrated to 3-5h under the conditions of 90-110 DEG C, -0.08MPa~-0.1MPa；It will dehydration
60 parts of 40 parts of DP-4000, BY3301 afterwards is added in reaction kettle, adjusts and constant temperature is at 40-60 DEG C, sequentially add Isosorbide-5-Nitrae-
8 parts of butanediol, 2 parts of trimethylolpropane, 0.5 part of water, 8,124 0.04 parts of BiCAT, 0.8 part of DC-193, sulfonate type chain extension
2 parts of agent A95, it is stirred 4-6h, obtains component A；
(2) component B is prepared:
It in 42 parts of investment reaction kettles of MDI-100 and will be uniformly mixed, dewatered DP-4000 20 be then added
Part, 20 parts of BY3301, are warming up to 70-80 DEG C, are stirred to react 4-6h, obtain component B；
(3) preparation of uninanned platform leather:
The KT3010 sulfonic acid type water-base resin of the aqueous Ke Tian Materials Co., Ltd in Hefei is coated in release paper, 130 DEG C dry
It forms within dry 2 minutes, obtains surface layer；Component A and component B is sufficiently mixed in low-pressure casting machine by 100/124 mass ratio, is obtained
Solvent-free polyurethane resin, and be poured be coated on aqueous covercoat on, subsequently into 110 DEG C baking oven pre-reaction 60 seconds, pre-reaction knot
Base fabric is bonded after beam, then the reaction was continued 7 minutes in 100-150 DEG C, forms its crosslinking curing；By release paper after curing molding
Removing, and wind, high removing uninanned platform leather is obtained, test peel strength (as initial bonding strength) is 94N/3cm, system
Uninanned platform leather again through 70 DEG C, post curing for 24 hours, test peel strength (as permanent peel strength) is 117N/3cm, 5
All peel strength retention rates (70 DEG C × 95% humidity) are 87%, deflect for room temperature 23 DEG C × 100,000 times not crack, resist cold -10 DEG C
It deflects not crack for × 8 ten thousand times.
Embodiment 3
(1) component A is prepared:
It is spare that DP-4000, BY3301 are dehydrated to 3-5h under the conditions of 90-110 DEG C, -0.08MPa~-0.1MPa；It will dehydration
30 parts of 70 parts of DP-4000, BY3301 afterwards is added in reaction kettle, adjusts and constant temperature is at 40-60 DEG C, sequentially add Isosorbide-5-Nitrae-
15 parts of butanediol, 0 part of trimethylolpropane, 1.5 parts of water, 8,124 0.05 parts of BiCAT, 2 parts of DC-193, sulfonate type chain extension
5 parts of agent A95, it is stirred 4-6h, obtains component A；
(2) component B is prepared:
It in 60 parts of investment reaction kettles of MDI-100 and will be uniformly mixed, dewatered DP-4000 30 be then added
Part, 10 parts of BY3301, are warming up to 70-80 DEG C, are stirred to react 4-6h, obtain component B；
(3) preparation of uninanned platform leather:
The KT3010 sulfonic acid type water-base resin of the aqueous Ke Tian Materials Co., Ltd in Hefei is coated in release paper, 130 DEG C dry
It forms within dry 2 minutes, obtains surface layer；Component A and component B is sufficiently mixed in low-pressure casting machine by 100/102 mass ratio, is obtained
Solvent-free polyurethane resin, and be poured be coated on aqueous covercoat on, subsequently into 110 DEG C baking oven pre-reaction 60 seconds, pre-reaction knot
Base fabric is bonded after beam, then the reaction was continued 7 minutes in 100-150 DEG C, forms its crosslinking curing；By release paper after curing molding
Removing, and wind, high removing uninanned platform leather is obtained, test peel strength (as initial bonding strength) is 121N/3cm,
For uninanned platform leather obtained again through 70 DEG C, post curing for 24 hours, test peel strength (as permanent peel strength) is 161N/
3cm, 5 weeks peel strength retention rate (70 DEG C × 95% humidity) be 85%, deflect not crack for room temperature 23 DEG C × 100,000 times, it is resistance to
It trembles with fear -10 DEG C × 80,000 times and deflects not crack.
Embodiment 4
(1) component A is prepared:
It is spare that DP-4000, BY3301 are dehydrated to 3-5h under the conditions of 90-110 DEG C, -0.08MPa~-0.1MPa；It will dehydration
60 parts of 40 parts of DP-4000, BY3301 afterwards is added in reaction kettle, adjusts and constant temperature is at 40-60 DEG C, sequentially add Isosorbide-5-Nitrae-
8 parts of butanediol, 2 parts of trimethylolpropane, 0.5 part of water, 8,124 0.04 parts of BiCAT, 0.8 part of DC-193, sulfonate type chain extension
1 part of agent A95, it is stirred 4-6h, obtains component A；
(2) component B is prepared:
It in 42 parts of investment reaction kettles of MDI-100 and will be uniformly mixed, dewatered DP-4000 20 be then added
Part, 20 parts of BY3301, are warming up to 70-80 DEG C, are stirred to react 4-6h, obtain component B；
(3) preparation of uninanned platform leather:
The KT3010 sulfonic acid type water-base resin of the aqueous Ke Tian Materials Co., Ltd in Hefei is coated in release paper, 130 DEG C dry
It forms within dry 2 minutes, obtains surface layer；Component A and component B is sufficiently mixed in low-pressure casting machine by 100/108 mass ratio, is obtained
Solvent-free polyurethane resin, and be poured be coated on aqueous covercoat on, subsequently into 110 DEG C baking oven pre-reaction 60 seconds, pre-reaction knot
Base fabric is bonded after beam, then the reaction was continued 7 minutes in 100-150 DEG C, forms its crosslinking curing；By release paper after curing molding
Removing, and wind, high removing uninanned platform leather is obtained, test peel strength (as initial bonding strength) is 86N/3cm, system
Uninanned platform leather again through 70 DEG C, post curing for 24 hours, test peel strength (as permanent peel strength) is 102N/3cm, 5
All peel strength retention rates (70 DEG C × 95% humidity) are 85%, deflect for room temperature 23 DEG C × 100,000 times not crack, resist cold -10 DEG C
It deflects not crack for × 8 ten thousand times.
Comparative example 1
(1) component A is prepared:
It is spare that DP-4000, BY3301 are dehydrated to 3-5h under the conditions of 90-110 DEG C, -0.08MPa~-0.1MPa；It will dehydration
60 parts of 40 parts of DP-4000, BY3301 afterwards is added in reaction kettle, adjusts and constant temperature is at 40-60 DEG C, sequentially add Isosorbide-5-Nitrae-
8 parts of butanediol, 2 parts of trimethylolpropane, 0.5 part of water, 8,124 0.04 parts of BiCAT, 0.8 part of DC-193, are stirred 4-
6h obtains component A；
(2) component B is prepared:
It in 42 parts of investment reaction kettles of MDI-100 and will be uniformly mixed, dewatered DP-4000 20 be then added
Part, 20 parts of BY3301, are warming up to 70-80 DEG C, are stirred to react 4-6h, obtain component B；
(3) preparation of uninanned platform leather:
The KT3010 sulfonic acid type water-base resin of the aqueous Ke Tian Materials Co., Ltd in Hefei is coated in release paper, 130 DEG C dry
It forms within dry 2 minutes, obtains surface layer；Component A and component B is sufficiently mixed in low-pressure casting machine by 100/101 mass ratio, is obtained
Solvent-free polyurethane resin, and be poured be coated on aqueous covercoat on, subsequently into 110 DEG C baking oven pre-reaction 60 seconds, pre-reaction knot
Base fabric is bonded after beam, then the reaction was continued 7 minutes in 100-150 DEG C, forms its crosslinking curing；By release paper after curing molding
Removing, and wind, high removing uninanned platform leather is obtained, test peel strength (as initial bonding strength) is 25N/3cm, system
Uninanned platform leather again through 70 DEG C, post curing for 24 hours, test peel strength (as permanent peel strength) is 31N/3cm, 5
All peel strength retention rates (70 DEG C × 95% humidity) are 88%, deflect for room temperature 23 DEG C × 100,000 times not crack, resist cold -10 DEG C
It deflects not crack for × 8 ten thousand times.
Comparative example 2
(1) component A is prepared:
It is spare that DP-4000, BY3301 are dehydrated to 3-5h under the conditions of 90-110 DEG C, -0.08MPa~-0.1MPa；It will dehydration
30 parts of 70 parts of DP-4000, BY3301 afterwards is added in reaction kettle, adjusts and constant temperature is at 40-60 DEG C, sequentially add Isosorbide-5-Nitrae-
15 parts of butanediol, 0 part of trimethylolpropane, 1.5 parts of water, 8,124 0.05 parts of BiCAT, 2 parts of DC-193, sulfonate type chain extension
5 parts of agent A95, it is stirred 4-6h, obtains component A；
(2) component B is prepared:
It in 60 parts of investment reaction kettles of MDI-100 and will be uniformly mixed, dewatered DP-4000 30 be then added
Part, 10 parts of BY3301, are warming up to 70-80 DEG C, are stirred to react 4-6h, obtain component B；
(3) preparation of uninanned platform leather:
The KTC716 carboxylic acid type water-base resin of the aqueous Ke Tian Materials Co., Ltd in Hefei is coated in release paper, 130 DEG C dry
It forms within dry 2 minutes, obtains surface layer；Component A and component B is sufficiently mixed in low-pressure casting machine by 100/102 mass ratio, is obtained
Solvent-free polyurethane resin, and be poured be coated on aqueous covercoat on, subsequently into 110 DEG C baking oven pre-reaction 60 seconds, pre-reaction knot
Base fabric is bonded after beam, then the reaction was continued 7 minutes in 100-150 DEG C, forms its crosslinking curing；By release paper after curing molding
Removing, and wind, high removing uninanned platform leather is obtained, test peel strength (as initial bonding strength) is 17N/3cm, system
Uninanned platform leather again through 70 DEG C, post curing for 24 hours, test peel strength (as permanent peel strength) is 35N/3cm, 5
All peel strength retention rates (70 DEG C × 95% humidity) are 75%, deflect for room temperature 23 DEG C × 100,000 times not crack, resist cold -10 DEG C
It deflects not crack for × 8 ten thousand times.
Table 1 is the formula composition and performance knot of the solvent-free polyurethane resin of Examples 1 to 4, comparative example 1 and comparative example 2
Fruit comparison.
As can be seen from Table 1: (1) embodiment 1-4 comparing with comparative example 1, embodiment 1-4 is greater than in comparative example 1
Initial bonding strength and permanent peel strength, it was demonstrated that it is aqueous that solvent-free polyurethane resin prepared by the present invention is applied to sulfonic acid type
On resin, initial bonding strength and permanent peel strength are greatly improved.
(2) it is aqueous to be applied to carboxylic acid type by comparative example 1-4 and comparative example 2 for solvent-free polyurethane resin of the invention
On resin, peel strength can not show a candle to apply the peel strength on sulfonic acid type water-base resin high, this is because carboxylic acid type is aqueous
The gel reaction of resin p-sulfonic acid type solvent-free polyurethane resin produces inhibiting effect.
The formula composition and results of property of the solvent-free polyurethane resin of 1 Examples 1 to 4 of table, comparative example 1 and comparative example 2
Claims (10)
1. a kind of solvent-free polyurethane resin, which is characterized in that mixed by component A and component B, wherein
In the component A, including 30-70 mass parts polyether polyol, 30-70 mass parts sulfonate polyester polyol, 5-15 matter
Measure part small molecule chain extender, 0-5 mass parts crosslinking agent and 0.1-1.5 mass parts water, 0.025-0.05 mass parts of catalyst, 0.1-
5 mass parts sulfonate type chain extenders, 0.1-2 mass parts foam stabiliser；
In the B component, including 10-30 mass parts polyether polyol, 10-30 mass parts sulfonate polyester polyol and 40-60
Mass parts isocyanates.
2. a kind of solvent-free polyurethane resin according to claim 1, it is characterised in that: the sulfonate type chain extender is
The addition product of Diaminoalkyl sulfonate or unsaturated dihydric alcohol and sodium hydrogensulfite.
3. a kind of solvent-free polyurethane resin according to claim 1, it is characterised in that: the polyether polyol is molecule
Measure one of polypropylene oxide glycol or the high activity polyether triol of molecular weight 5000~6000 of 1000-2000.
4. a kind of solvent-free polyurethane resin according to claim 1, it is characterised in that: the sulfonate polyester polyol
Molecular weight be 1000-2000.
5. a kind of solvent-free polyurethane resin according to claim 1, it is characterised in that: the sulfonate polyester polyol
It is sulfonated obtained to pass through dehydrating polycondensation in parts by weight by following components: 40-80 parts of adipic acid, 30-60 parts of small molecule dihydric alcohol,
0.01-0.06 parts of tetrabutyl titanate catalyst, polyester polyol is made through sulfonated and obtains sulfonate polyester polyol.
6. a kind of solvent-free polyurethane resin according to claim 1, it is characterised in that: the small molecule chain extender is two
Ethanol amine, ethylenediamine, ethylene glycol, 1,2-PD, 1,3-PD, 1,4-butanediol, 1,5-PD, neopentyl glycol, one
Diglycol ethylene, dipropylene glycol, 3- methyl-1,5- pentanediol, 1,6- hexylene glycol, 1,4-CHDM quinhydrones are double
One or more of (2- ethoxy) ether.
7. a kind of solvent-free polyurethane resin according to claim 1, it is characterised in that: the crosslinking agent be glycerine,
One or more of trimethylolpropane, triethanolamine.
8. a kind of solvent-free polyurethane resin according to claim 1, it is characterised in that: the catalyst is BiCAT
8106、BiCAT 8108、BiCAT 8124、BiCAT 3228、Borchi Kat 22、Borchi Kat 24、BiCAT 4130、
The phenolate of BiCAT 4232, MB20 and above-mentioned organometallic catalysts, formates, hydrochloride, DBU, triethylene triamine, A1
One or more of and in the phenolate of above-mentioned amines catalyst, formates, ethylhexanoate salt.
9. a kind of solvent-free polyurethane resin according to claim 1, it is characterised in that: the foam stabiliser is polyethers
Modified silicone surfactants.
10. a kind of application of such as described in any item solvent-free polyurethane resins of claim 1-9, which is characterized in that the nothing
Solvent polyurethane resin is applied to sulfonic acid type water-base resin.
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| CN114892412A (en) * | 2022-06-02 | 2022-08-12 | 浙江昶丰新材料有限公司 | High-filler solvent-free water-based synthetic leather and preparation method thereof |
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| CN110964172A (en) * | 2019-11-06 | 2020-04-07 | 合肥科天水性科技有限责任公司 | Modified solvent-free bio-based polyurethane resin and application thereof |
| CN110964172B (en) * | 2019-11-06 | 2021-11-23 | 合肥科天水性科技有限责任公司 | Modified solvent-free bio-based polyurethane resin and application thereof |
| CN110951033A (en) * | 2019-12-19 | 2020-04-03 | 超然(福建)新材料科技有限公司 | Hydrolysis-resistant polyurethane resin and preparation method thereof |
| CN114892412A (en) * | 2022-06-02 | 2022-08-12 | 浙江昶丰新材料有限公司 | High-filler solvent-free water-based synthetic leather and preparation method thereof |
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