CN108215366A - Solventfree resin and preparation method thereof, reagent preparation box and application - Google Patents
Solventfree resin and preparation method thereof, reagent preparation box and application Download PDFInfo
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- CN108215366A CN108215366A CN201711476111.XA CN201711476111A CN108215366A CN 108215366 A CN108215366 A CN 108215366A CN 201711476111 A CN201711476111 A CN 201711476111A CN 108215366 A CN108215366 A CN 108215366A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/06—Interconnection of layers permitting easy separation
-
- 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
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- 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
- C08G18/44—Polycarbonates
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
-
- 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
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
Abstract
The invention discloses a kind of solventfree resin and preparation method thereof, reagent preparation box and applications.The preparation method of solventfree resin, 1）Preparation A material isocyanate prepolymers, 2）B material polyol blends are prepared, B material include 100 parts of polyalcohol, 0.1 15 parts of crosslinking agent, 0.1 5 parts of surfactant, 0.01 2 parts of catalyst, and 3）By A material and B material mixing, by mass parts, A expects 20 200 parts, and B expects 100 parts, for being coated with.Solventfree resin is used to prepare no-solvent type fabric.The kit of solventfree resin includes the A material and B material；Or including being used to prepare the raw material of A material and B material；Or the raw material including A material and for preparing B material.Solventfree resin is free from moisture, the resin for not containing plasticizer, not containing organic solvent, is a kind of resin being made of curable composition.The present invention can once be coated with finished surface layer and bond the no-solvent type resin of layer function, simplify production technology, take into account the feature of environmental protection and economy without using any organic solvent.
Description
Technical field
The present invention relates to a kind of solventfree resin and preparation method thereof, reagent preparation box and applications.
Background technology
The feel of the existing natural leather of dermatine, and the shortcomings that overcome natural leather, so in sofa, chair, case
It is widely applied on the various consumer goods such as packet, shoes, automobile cushion and built-in material and industrial products.
The main material of existing dermatine is polyvinyl chloride（PVC）, silicon（Silicone）, polyurethane
（Polyurethane）Deng polyvinyl chloride in the market（PVC）It is relatively broad with the use of polyurethane.But during using PVC, it is
Soft-touch, it is necessary to use plasticizer（Plasticizer), part plasticizer has detected environmentally harmful ingredient, therefore
The usage amount of PVC is fewer and fewer, and the usage amount of polyurethane increasingly expands.
Dermatine polyurethane can be divided into solvent type resin（solventborne resins）With no-solvent type resin
（Solvent-free resins）.The conventionally manufactured mode of dermatine is in release paper coated thereon solvent type face layer
（skin）It is dry after resin, solvent type adhesive layer resin is then coated again, is waited after a certain period of time, then compound.
Dermatine needs possess the sense of touch similar with natural leather, while also to overcome the physical property shortcoming of natural leather,
In order to meet these conditions, it is desirable that molecular resin amount is usually more than 30000, but molecular resin amount is bigger, and viscosity is often
Increase simultaneously, high viscosity can cause resin that cannot directly use, thus it is common to use solvent carrys out dissolving resin, reduce viscosity.With
Solvent based on dimethylformamide (DMF, dimethylformamide), commonly used to dissolving resin；Butanone（MEK,
Methyl ethyl ketone), acetone (acetone), ethyl acetate（EA, ethyl acetate), toluene（toluene）
Etc. various solvents, it is generally mated DMF and uses to reduce viscosity or dissolving resin.But when human body sucking DMF or long skin
Between if contact DMF, the damage of the internal organ such as liver kidney can be led to, therefore, various countries strictly limit or ban harmful molten
The use of agent.
Usual solvents mass percent accounts for the 30-70% of naval stores.At present, in industry, the no-solvent type of broad sense is divided into water
Dissolubility type（Water base type), high solids content type（High-solid type), not card-type（MOCA, 4,4-
Methylene bis (2-chloroaniline) type, no DMF types（DMF free type）.Although water-soluble type does not make
With organic solvents such as DMF, using water as dissolving medium, but in terms of the technique for applying of product, with it is existing it is solvent type should
It is more similar with technique.Moreover, the product of part aqueous type, in order to preferably dissolve polyurethane resin, still using 3-
The organic solvents such as 10% DMF or NMP, but it is water-soluble products also to call oneself.The processing temperature of high solids content type will be to 150
Degree causes processing to be not easy, and the viscosity of resin in itself is higher, in order to reduce viscosity, generally requires the organic molten of 3-10%
Agent still, equally also calls oneself solvent-free products.The primary raw material MOCA of card-type is classified by Environmental Protection Agency USA (EPA)
For one of most harmful chemical substance, harmful chemical substance, therefore used by limitation.The resin of DMF free type
Although product without using DMF solvent, equally uses other organic solvents.
Invention content
In order to overcome the problems of the prior art, the present invention provides a kind of solventfree resin and preparation method thereof, prepare
Kit and application.Heretofore described solventfree resin, refer in particular to not contain moisture, do not contain plasticizer, do not contain it is organic
The resin of solvent is the resin that a kind of curable composition by 100% forms briefly.Solventfree resin completely do not include pair
The solvent composition that human body and environment are harmful to, and possess the resin of face layer and bonding layer function simultaneously, it can be one or many
Direct coated and molded, therefore simple for process, to human body, environmentally friendly.
A kind of preparation method of solventfree resin,
1）A material isocyanate prepolymers are prepared,
Pass through isocyanates and polyalcohol（Polyol）A material isocyanate prepolymers, during A expects, NCO content 10- is obtained by the reaction
24%, 25 degrees Celsius of lower viscosity are 200-10000 centipoises（cp)；
The functional group of the polyalcohol is 2-3, molecular weight 500-6000, and the polyalcohol is selected from polyester polyol
（polyester polyol）, polyether polyol（polyether polyol）, polyester and polyether polyalcohol（polyester/
ether copolyol）, polytetramethylene ether diol（PTMEG, polyetramethylene ether glycol）, gather
Carbonate diol（polycarbonatediol）, poly-lactone polyol（polylactone polyol）In one kind or more
Kind；
2）B material polyol blends are prepared,
In B material, by mass parts, including the polyalcohol（polyol）100 parts, 0.1-15 parts of crosslinking agent, surfactant
0.1-5 parts, 0.01-2 parts of catalyst；It is obtained after being stirred 30 minutes at 50-60 degrees Celsius；
3）By A material and B material mixing, by mass parts, A expects 20-200 parts, and B expects 100 parts, for being coated with.
Further, 4）It is coated in release paper, is placed in baking oven and is dried, in partial desiccation state, exist with cloth
It is compound under pressure.
The isocyanates, selected from 2,4- toluene di-isocyanate(TDI)s（2,4-toluene diisocyanate）, 2,6-
Toluene di-isocyanate(TDI)（2,6-toluene diisocyanate), toluene di-isocyanate(TDI)（TDI, toluene
), diisocyanate methylenediphenyl diisocyanates（Methylene diphenyl diisocyanate, MDI）, six
Methylene diisocyanate (HDI, hexamethylene diisocyanate), isophorone diisocyanate（IPDI,
Isophorone diisocyanate), hydrogenation methylenebis phenyl isocyanate (H12-MDI, dicyclohexylmethane
One or more of diisocyanate), the MDI includes pure MDI（pure-MDI）, it is denaturalized MDI（modified-
MDI）, polymeric MDI (polymer-MDI).
The polyester polyol（Polyester polyol）It is by polybinary acid（Multi diacid) and more second
Glycol（multi glycol）Concentration polymerization（condensation polymerization）It is obtained by the reaction, molecular weight 500-
6000；The binary acid（diacid）, selected from adipic acid (adipic acid), glutaric acid（glutaric acid）, amber
Amber acid（succinic acid）, phthalic acid（phtalic acid）, phthalic anhydride（phthalic
anhydride）, M-phthalic acid（isophthalic acid）, terephthalic acid (TPA)（terephthalic acid）In one
Kind is a variety of；More ethylene glycol, selected from ethylene glycol（EG, ethylene glycol）, diethylene glycol (DEG)（DEG,
diethylene glycol）, 1,4- butanediols（1,4-BD, 1,4-butanediol）, 1,6-HD（1,6-HD, 1,
6-hexanediol）, 1,2- butanediols（1,2-BD, 1,2-butanediol）, 1,3 butylene glycol（1,3-BD, 1,3-
butanediol）, 1,2- propylene glycol（1,2-propanediol）, 1,3- propylene glycol（1,3-propanediol）, dipropyl two
Alcohol（DPG, dipropylene glycol）, tripropylene glycol（TPG, tripropylene glycol）, propylene glycol（PG,
propylene glycol）, trimethylolpropane（TMP, trimethylolpropane）, glycerine（glycerine）In
It is one or more kinds of.
The crosslinking agent, selected from ethylene glycol（EG, ethylene glycol), diethylene glycol (DEG) (DEG, diethlene
Glycol), 1,4-butanediol (Isosorbide-5-Nitrae-BD, Isosorbide-5-Nitrae-butanediol), 1,6- hexylene glycol (1,6-HD, 1,6-
Hexanediol), 1,2- butanediols (1,2-BD, 1,2-butanediol), 1,3-BDO (1,3-BD, 1,3-
), butanediol 1,2- propylene glycol (1,2-propanediol), 1,3- propylene glycol (1,3-propanediol), dipropyl two
Alcohol (DPG, dipropylene glycol), tripropylene glycol (TPG, tripropylene glycol), Propylene Glycol
(PG, propylene glycol), trimethylolpropane (TMP, trimethylolpropane), glycerine
One or more of (glycerine).
The surfactant is Siloxane-Oxyalkylene Copolymers（ polyether modified polysiloxane）.
The catalyst is using amine and/or the catalyst of the heat sensitivity of metal；The metallic catalyst packet
Include dibutyl tin laurate（ Dibutyltindilaurate）, stannous octoate（stannous octoate）, zinc polycarboxylate
（zinc carboxylate）, capric acid bismuth（bismuth decanoate）, the amines catalyst (amine
Catalyst) including the dilute diamines of three second（TEDA, triethylenediamine）, N-ethylmorpholine（N-
ethylmorpholine）, DMIZ 1,2 dimethylimidazole（1,2-dime imidazole）, N-（N', N'-2- dimethylamino second
Base）Morpholine（N-(N',N'-2-dimethylamino ethyl)morpholine）.
Step 2）The B material further comprise 10-200 parts of mill base.
The solventfree resin that a kind of preparation method described in basis obtains.
A kind of application of the solventfree resin, is used to prepare no-solvent type fabric.
A kind of kit for being used to prepare the solventfree resin, including the A material and B material；Or including use
In the raw material and B material of preparing A material；Or the raw material including A material and for preparing B material.
Beneficial effects of the present invention
The present invention does not use any organic solvent, can once be coated with finished surface layer and bond the no-solvent type resin of layer function,
From traditional approach（By twice or above coating, being respectively completed the coating of solvent type surface layer resin and solvent type adhesive layer tree
The mode of fat coating）, production technology is simplified, is improved as novel environmentally friendly mode（Primary or multiple coating no-solvent type tree
Fat, while possess the mode of face layer and bonding layer function）So that artificial leather/synthetic leather product takes into account the feature of environmental protection and economy.
Specific embodiment
The present invention is further elaborated with reference to embodiments.
A kind of preparation method of solventfree resin,
1）A material isocyanate prepolymers are prepared,
Pass through isocyanates and polyalcohol（Polyol）A material isocyanate prepolymers, during A expects, NCO content 10- is obtained by the reaction
24%, 25 degrees Celsius of lower viscosity are 200-10000 centipoises（cp).
If the content of NCO is too low, viscosity can be caused to greatly improve, be difficult to use face layer.If the content of NCO is more than
24%, viscosity is too low, cannot form surface thickness, and leads to hardness height, it is also difficult to realize the feel of natural leather.If
It only limits the use of in adhesive, the content of isocyanates is about 10% also out of question.
If the viscosity of isocyanate prepolymer is excessively high, mobility reduces, and fabric penetrability occurs and declines.Conversely, viscosity
Too low, cortex is difficult to thicken, and raw material excessively sees through fabric.Therefore, the viscosity of isocyanate prepolymer is 200 to 10000 lis
Moor proper, A material are usually liquid at normal temperatures, but under given conditions（For example low temperature has been received in advance）May also be
Solid state, it is therefore possible to be used after needing dissolving, viscosity-adjusting agent to 500-5000 centipoises uses relatively good.
The polyalcohol is selected from polyester polyol（polyester polyol）, polyether polyol（polyether
polyol）, polyester and polyether polyalcohol（Polyester/ether copolyol, polyester polyol and polyether polyol are total to
Polymers can be mixing physically, can also make combination chemically）, polytetramethylene ether diol（PTMEG,
polyetramethylene ether glycol）, polycarbonate glycol（polycarbonatediol）, polylactone is polynary
Alcohol（polylactone polyol）In it is one or more.
The functional group of the polyalcohol is 2-3, molecular weight 500-6000.If the average functional group of polyester polyol
If lower than above-mentioned range, molecule is not grown up fully, can feel hard, and tensile strength（tensil stength）,
Tearing strength（tear strength）Etc. physical properties can decline, if if functional group is higher than above-mentioned range, it may occur that physics
The problems such as characteristic declines or excess stickiness is high, causes to be not easy to apply.
2）B material polyol blends are prepared,
In B material, by mass parts, including the polyalcohol（polyol）100 parts, 0.1-15 parts of crosslinking agent, surfactant
0.1-5 parts, 0.01-2 parts of catalyst；It is obtained after being stirred 30 minutes at 50-60 degrees Celsius；
3）By A material and B material mixing, by mass parts, A expects 20-200 parts, and B expects 100 parts, for being coated with.
Further, 4）It is coated in release paper, is placed in baking oven and is dried, in partial desiccation state, exist with cloth
It is compound under pressure.
The isocyanates, selected from 2,4- toluene di-isocyanate(TDI)s（2,4-toluene diisocyanate）, 2,6-
Toluene di-isocyanate(TDI)（2,6-toluene diisocyanate), toluene di-isocyanate(TDI)（TDI, toluene
), diisocyanate methylenediphenyl diisocyanates（Methylene diphenyl diisocyanate, MDI）, six
Methylene diisocyanate (HDI, hexamethylene diisocyanate), isophorone diisocyanate（IPDI,
Isophorone diisocyanate), hydrogenation methylenebis phenyl isocyanate (H12-MDI, dicyclohexylmethane
One or more of diisocyanate), the MDI includes pure MDI（pure-MDI）, it is denaturalized MDI（modified-
MDI）, polymeric MDI (polymer-MDI).Light turns yellow in order to prevent, IPDI, the HDI that yellowing resistance can be used outstanding,
H12-MDI etc..
The polyester polyol（Polyester polyol）It is by polybinary acid（Multi diacid) and more second
Glycol（multi glycol）Concentration polymerization（condensation polymerization）It is obtained by the reaction, molecular weight 500-
6000.If the average functional group of polyester polyol is lower than above-mentioned range, molecule growth is insufficient to lead to harder feel, drop
The problem of physical properties such as low tearing strength.If functional group is more excessively high than above range, physical property, which can also occur, to be reduced or glues
The problem of high is spent, causes to be not easy to use.For molecular weight below 500, feel is harder, it is difficult to realize the soft of dermatine
It is soft, if more than 6000 molecular weight, generate excessively soft or stick glutinous feel, and may be excessively high because of viscosity, cause not allowing
Easily use.
The binary acid（diacid）, selected from adipic acid (adipic acid), glutaric acid（glutaric acid）,
Succinic acid（succinic acid）, phthalic acid（phtalic acid）, phthalic anhydride（phthalic
anhydride）, M-phthalic acid（isophthalic acid）, terephthalic acid (TPA)（terephthalic acid）In one
Kind is a variety of；
More ethylene glycol, selected from ethylene glycol（EG, ethylene glycol）, diethylene glycol (DEG)（DEG, diethylene
glycol）, 1,4- butanediols（1,4-BD, 1,4-butanediol）, 1,6-HD（1,6-HD, 1,6-
hexanediol）, 1,2- butanediols（1,2-BD, 1,2-butanediol）, 1,3 butylene glycol（1,3-BD, 1,3-
butanediol）, 1,2- propylene glycol（1,2-propanediol）, 1,3- propylene glycol（1,3-propanediol）, dipropyl two
Alcohol（DPG, dipropylene glycol）, tripropylene glycol（TPG, tripropylene glycol）, propylene glycol（PG,
propylene glycol）, trimethylolpropane（TMP, trimethylolpropane）, glycerine（glycerine）In
It is one or more kinds of.
The crosslinking agent, selected from ethylene glycol（EG, ethylene glycol), diethylene glycol (DEG) (DEG, diethlene
Glycol), 1,4-butanediol (Isosorbide-5-Nitrae-BD, Isosorbide-5-Nitrae-butanediol), 1,6- hexylene glycol (1,6-HD, 1,6-
Hexanediol), 1,2- butanediols (1,2-BD, 1,2-butanediol), 1,3-BDO (1,3-BD, 1,3-
), butanediol 1,2- propylene glycol (1,2-propanediol), 1,3- propylene glycol (1,3-propanediol), dipropylene glycol
(DPG, dipropylene glycol), tripropylene glycol (TPG, tripropylene glycol), Propylene Glycol (PG,
Propylene glycol), trimethylolpropane (TMP, trimethylolpropane), in glycerine (glycerine)
One or more.Crosslinking agent is according to the physical property requirement of solventfree resin, such as modulus（modulus）, tensile strength（
tensile strength）Tearing strength (tear strength) extends (elongation) etc. to select to use.
The purpose of surfactant is to improve the diffusivity of solventfree resin, lubricity, wearability, feel is added,
Siloxane-Oxyalkylene Copolymers can be used in the surfactant（ polyether modified polysiloxane）.
The catalyst uses the heat sensitivity of amine and/or metal（thermal sensitivity
catalyst）Catalyst（thermal sensitivity catalyst）；The metallic catalyst includes tin dilaurate
Dibutyl tin（ Dibutyltindilaurate）, stannous octoate（stannous octoate）, zinc polycarboxylate（zinc
carboxylate）, capric acid bismuth（bismuth decanoate）Wait tin class (Tin), zinc class (Zinc), bismuth class (Bismuth)
Catalyst, the amines catalyst (amine catalyst) include the dilute diamines of three second（TEDA,
triethylenediamine）, N-ethylmorpholine（N-ethylmorpholine）, DMIZ 1,2 dimethylimidazole（1,2-dime
imidazole）, N-（N', N'-2- dimethylaminoethyl）Morpholine（N-(N',N'-2-dimethylamino ethyl)
morpholine）.Catalyst can dilute use when necessary.Polyester catalyst divides into kicker (blowing
) and gel catalyst catalyst（gelling catalyst）, can also divide into cold(-)setting and thermmohardening catalysis.The present invention
In view of hardening（Curing）Temperature 100-150 degree, firm time are generally within 1 minute to 10 minutes.Kicker and solidifying
Glue catalyst can be used alone, and also use simultaneously, while using then with fretting map performance and thermosetting energy.
Step 2）The B material further comprise 10-200 parts of mill base.The use of mill base can realize coating surface
The diversity of color.The addition of mill base, according to whether depending on the type of color and color, this is those skilled in the art
Conventional wisdom.
Other additives (additives) are applicable according to the purposes of fabric, are mainly applicable in antioxidant
（), antioxidant color inhibition agent (UV absorber) etc..
The solventfree resin that a kind of preparation method described in basis obtains.
A kind of application of the solventfree resin, is used to prepare no-solvent type fabric.The fabric include dermatine,
Synthetic leather, super fiber leather etc..
A kind of kit for being used to prepare the solventfree resin, including the A material and B material；Or including use
In the raw material and B material of preparing A material；Or the raw material including A material and for preparing B material.For those skilled in the art
For, if obtained A material expects this combination with B, it is possible to be relatively easy to and prepare solventfree resin.
By the introduction of following embodiment, those skilled in the art can more directly implement the present invention, but these are implemented
Example is not intended to limit the invention, and can obviously make a variety of changes and change to those skilled in the art
Type.
Embodiment 1（The preparation of A material 1）
Pure MDI is added in the flask of nitrogen charging（4,4- methyl diphenylene diisocyanates, 4,4-
diphenylmethanediisocyanate）It 522.3 grams, is completely dissolved at 50-60 degrees Celsius.After confirmation is completely dissolved, add
Enter to be denaturalized 104.5 grams of MDI (modified-MDI), ester polyol（ester polyol ）373.2g, wherein ester polyol points
Son amount is 2000, constituent AA（Adipic acid, adipic acid）, EG, DEG, be in mass ratio AA：EG：DEG=60：
20：20, it is sequentially added into, is maintained at 72-78 degrees Celsius of three hour synthesis.The NCO% of product A material 1 is 19%, viscosity 500
To 2000 centipoises（25 degrees Celsius）.
Embodiment 2-5（A expects the preparation of 2-5）
It is synthesized with reference to the method for embodiment 1, but independent or two type combination of the above, polyalcohol may be used in isocyanates
Independent or two type combination of the above reactions mode may be used to manufacture.Reaction condition is referred to embodiment 1, according to different
The type of cyanate, the type of polyalcohol and molecular weight carry out respective change.
The results are shown in Table 1 by embodiment 1-5.
Embodiment 6（The synthesis of B material 1）
Polyester polyol is added in the flask of nitrogen charging（polyesterpolyol）(molecular weight 1,000, constituent：AA
（Adipic acid, adipic acid）, EG, Isosorbide-5-Nitrae-BG（1,4-butanediol）) 445 grams, in mass ratio wherein AA：EG：Isosorbide-5-Nitrae-BG=
500：200：300, polyester polyol（polyester polyol）(molecular weight 2,000, constituent：AA, EG, Isosorbide-5-Nitrae-
BG）After 445 grams, in 105 degrees Celsius of vacuum decompressions（Vacuum), such state maintains a hour, this is removed in the process
After falling remaining moisture, 80 grams of Isosorbide-5-Nitrae-BG is added in, after 30 grams of surfactant, 0.8 gram of catalyst, in 50-60 degrees Celsius of stirring
It is obtained after 30 minutes.
Embodiment 7-10（B expects the synthesis of 2-5）
It is synthesized with reference to 6 method of embodiment, but the polyalcohol of the inside（polyol）Using independent or two type combination of the above, crosslinking
If agent, independent or two type combination of the above can be used.
The results are shown in Table 2 by embodiment 6-10.
The manufacture of Application Example no-solvent type dermatine
Traditional solvent type dermatine manufacturing method is to include 30-40% solid contents in release paper coated thereon
（Solidcontent surface layer resin) after placing drying in 40-90 seconds in 90-120 degrees Celsius of baking oven, is coated with solid content
For the adhesive layer resin of 60-70%, after 60-120 seconds in 90-120 degrees Celsius of baking oven, partial desiccation（Semi-dry after), with
Cloth is compound at a certain pressure, after baking oven placement long period of time：1）It directly removes, obtains with release paper
Artificial leather product；Or 2）By specific temperature and time curing and then with release paper glass, obtain artificial leather product.
The B material that the present invention is prepared from the embodiment 1-5 A material isocyanate prepolymers being prepared and embodiment 6-10
After polyol blends are according to stoichiometry（The results are shown in Table 3）, stirred 30-60 seconds and carried out with blender 500-1000rpm
It is sufficiently mixed, is then coated on above release paper, be placed in 125 degrees Celsius of baking oven and be dried, arrived by 30 seconds 1 minute
It is 30 seconds 3 minutes, compound with being carried out under the pressure of 5-6kg/cm2 with cloth in partial desiccation state, by 12-48 hours, in 60-
Maturation manufactures in 90 degrees Celsius of hot cells.
Claims (11)
1. a kind of preparation method of solventfree resin, which is characterized in that
1）A material isocyanate prepolymers are prepared,
Pass through isocyanates and polyalcohol（Polyol）A material isocyanate prepolymers, during A expects, NCO content 10- is obtained by the reaction
24%, 25 degrees Celsius of lower viscosity are 200-10000 centipoises（cp)；
The functional group of the polyalcohol is 2-3, molecular weight 500-6000, and the polyalcohol is selected from polyester polyol
（polyester polyol）, polyether polyol（polyether polyol）, polyester and polyether polyalcohol（polyester/
ether copolyol）, polytetramethylene ether diol（PTMEG, polyetramethylene ether glycol）, poly- carbon
Acid esters glycol（polycarbonatediol）, poly-lactone polyol（polylactone polyol）In it is one or more；
2）B material polyol blends are prepared,
In B material, by mass parts, including the polyalcohol（polyol）100 parts, 0.1-15 parts of crosslinking agent, surfactant
0.1-5 parts, 0.01-2 parts of catalyst；It is obtained after being stirred 30 minutes at 50-60 degrees Celsius；
3）By A material and B material mixing, by mass parts, A expects 20-200 parts, and B expects 100 parts, for being coated with.
2. preparation method according to claim 1, which is characterized in that further, 4）It is coated in release paper, is placed on baking
It is dried in case, it is compound under stress with cloth in partial desiccation state.
3. preparation method according to claim 1, which is characterized in that the isocyanates, it is different selected from 2,4- toluene two
Cyanate（2,4-toluene diisocyanate）, 2,6- toluene di-isocyanate(TDI)s（2,6-toluene
Diisocyanate), toluene di-isocyanate(TDI)（TDI, toluene diisocyanate), methylenediphenyl diisocyanate
Ester（Methylene diphenyl diisocyanate, MDI）, hexamethylene diisocyanate (HDI, hexamethylene
Diisocyanate), isophorone diisocyanate（IPDI, isophorone diisocyanate), hydrogenate phenylmethane two
One or more of isocyanates (H12-MDI, dicyclohexylmethane diisocyanate), the MDI
Including pure MDI（pure-MDI）, it is denaturalized MDI（modified-MDI）, polymeric MDI (polymer-MDI).
4. preparation method according to claim 1, which is characterized in that the polyester polyol（Polyester
polyol）It is by polybinary acid（Multi diacid) and more ethylene glycol（multi glycol）Concentration polymerization
（condensation polymerization）It is obtained by the reaction, molecular weight 500-6000；
The binary acid（diacid）, selected from adipic acid (adipic acid), glutaric acid（glutaric acid）, succinic acid
（succinic acid）, phthalic acid（phtalic acid）, phthalic anhydride（phthalic anhydride）,
Phthalic acid（isophthalic acid）, terephthalic acid (TPA)（terephthalic acid）One or more of；
More ethylene glycol, selected from ethylene glycol（EG, ethylene glycol）, diethylene glycol (DEG)（DEG, diethylene
glycol）, 1,4-butanediol（1,4-BD, 1,4-butanediol）, 1,6- hexylene glycol（1,6-HD, 1,6-
hexanediol）, 1,2- butanediol（1,2-BD, 1,2-butanediol）, 1,3-BDO（1,3-BD, 1,3-
butanediol）, 1,2-PD（1,2-propanediol）, 1,3-PD（1,3-propanediol）, dipropylene glycol
（DPG, dipropylene glycol）, tripropylene glycol（TPG, tripropylene glycol）, propylene glycol（PG,
propylene glycol）, trimethylolpropane（TMP, trimethylolpropane）, glycerine（glycerine）In one
Kind is a variety of.
5. preparation method according to claim 1, which is characterized in that
The crosslinking agent, selected from ethylene glycol（EG, ethylene glycol), diethylene glycol (DEG) (DEG, diethlene
Glycol), 1,4-butanediol (Isosorbide-5-Nitrae-BD, Isosorbide-5-Nitrae-butanediol), 1,6- hexylene glycol (1,6-HD, 1,6-
Hexanediol), 1,2- butanediols (1,2-BD, 1,2-butanediol), 1,3-BDO (1,3-BD, 1,3-
Butanediol), 1,2-PD (1,2-propanediol), 1,3-PD (1,3-propanediol), dipropylene glycol
(DPG, dipropylene glycol), tripropylene glycol (TPG, tripropylene glycol), Propylene Glycol (PG,
Propylene glycol), trimethylolpropane (TMP, trimethylolpropane), in glycerine (glycerine)
It is one or more kinds of.
6. preparation method according to claim 1, which is characterized in that the surfactant is polyether-modified poly- silica
Alkane（ polyether modified polysiloxane）.
7. preparation method according to claim 1, which is characterized in that the catalyst uses amine and/or metal
Heat sensitivity catalyst；The metallic catalyst includes dibutyl tin laurate（
Dibutyltindilaurate）, stannous octoate（stannous octoate）, zinc polycarboxylate（zinc carboxylate）, capric acid
Bismuth（bismuth decanoate）, the amines catalyst (amine catalyst) includes the dilute diamines of three second（TEDA,
triethylenediamine）, N-ethylmorpholine（N-ethylmorpholine）, 1,2- methylimidazole（1,2-dime
imidazole）, N-（N', N'-2- dimethylaminoethyl）Morpholine（N-(N',N'-2-dimethylamino ethyl)
morpholine）.
8. preparation method according to claim 1, which is characterized in that step 2）The B material further comprise mill base
10-200 parts.
9. a kind of solventfree resin obtained according to claim 1-8 any one of them preparation methods.
10. a kind of application of solventfree resin according to claim 9, which is characterized in that be used to prepare no-solvent type face
Material.
11. a kind of kit for being used to prepare solventfree resin according to claim 9, which is characterized in that including described
A material and B material；Or including being used to prepare the raw material of A material and B material；Or the original including A material and for preparing B material
Material.
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| CN201711476111.XA CN108215366A (en) | 2017-12-29 | 2017-12-29 | Solventfree resin and preparation method thereof, reagent preparation box and application |
| PCT/CN2018/115755 WO2019128520A1 (en) | 2017-12-29 | 2018-11-15 | Solvent-free resin and preparation method therefor, preparation kit and use thereof |
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| WO2019128520A1 (en) * | 2017-12-29 | 2019-07-04 | 三星聚合物有限公司 | Solvent-free resin and preparation method therefor, preparation kit and use thereof |
| CN111187566A (en) * | 2020-02-24 | 2020-05-22 | 顺缔高新材料江苏有限公司 | Solvent-free self-leveling polyurethane wear-resistant material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101137506A (en) * | 2005-03-17 | 2008-03-05 | 巴斯福股份公司 | Method for producing polyurethane layers and use thereof as imitation leather |
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| CN102965064B (en) * | 2012-11-27 | 2014-03-19 | 上海汇得化工有限公司 | Preparation method and applications of solvent-free polyurethane adhesive |
| CN102994035B (en) * | 2012-12-06 | 2014-06-18 | 常熟国和新材料有限公司 | Solvent-free polyurethane adhesive coated at normal temperature and preparation method thereof |
| CN103525078B (en) * | 2013-10-09 | 2016-03-02 | 旭川化学（苏州）有限公司 | A kind of footwear leather environment-friendly type solvent-free foaming bed material and preparation method thereof |
| CN103497302A (en) * | 2013-10-10 | 2014-01-08 | 旭川化学（苏州）有限公司 | Environment-friendly solvent-free foaming base material for sofa leather and preparation method thereof |
| CN104072715B (en) * | 2014-07-07 | 2016-09-28 | 旭川化学（苏州）有限公司 | Solvent-free environment-friendly polyurethane automobile leather foaming layer resin and its preparation method and application |
| CN105969289B (en) * | 2016-05-17 | 2019-05-21 | 杨川 | A kind of high wettability package compound solventless adhesive and preparation method thereof |
| CN108215366A (en) * | 2017-12-29 | 2018-06-29 | 三星聚合物有限公司 | Solventfree resin and preparation method thereof, reagent preparation box and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101137506A (en) * | 2005-03-17 | 2008-03-05 | 巴斯福股份公司 | Method for producing polyurethane layers and use thereof as imitation leather |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019128520A1 (en) * | 2017-12-29 | 2019-07-04 | 三星聚合物有限公司 | Solvent-free resin and preparation method therefor, preparation kit and use thereof |
| CN111187566A (en) * | 2020-02-24 | 2020-05-22 | 顺缔高新材料江苏有限公司 | Solvent-free self-leveling polyurethane wear-resistant material and preparation method thereof |
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