CN106084178A - crosslinking agent - Google Patents

crosslinking agent Download PDF

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Publication number
CN106084178A
CN106084178A CN201510565568.2A CN201510565568A CN106084178A CN 106084178 A CN106084178 A CN 106084178A CN 201510565568 A CN201510565568 A CN 201510565568A CN 106084178 A CN106084178 A CN 106084178A
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clay
compound
linking agent
dihydric
cross
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郑国樑
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Individual
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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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • 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
    • C08G18/3225—Polyamines
    • C08G18/3234—Polyamines cycloaliphatic
    • 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
    • C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
    • C08G18/3895—Inorganic compounds, e.g. aqueous alkalimetalsilicate solutions; Organic derivatives thereof containing no direct silicon-carbon bonds
    • 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
    • C08G18/65—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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7806—Nitrogen containing -N-C=0 groups
    • C08G18/7843—Nitrogen containing -N-C=0 groups containing urethane 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/504—Amines containing an atom other than nitrogen belonging to the amine group, carbon and hydrogen

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

A crosslinking agent comprising a polymer having an amino group prepared by a first polymerization reaction of a first component comprising a clay-polyurethane having an isocyanate group and a diamine compound. The clay-polyurethane having an isocyanate group is prepared by a second polymerization reaction of a second component comprising a clay-polyurethane having at least a dihydroxy group with a weight average molecular weight of 2000 or less and a first polyisocyanate compound. The clay-polyurethane having at least a dihydroxy group is prepared by a third polymerization reaction of a third component comprising a clay having a dihydroxy group, a polyol compound having a molecular weight in the range of 700 or less and a second polyisocyanate compound having a molecular weight in the range of 300 or less. The cross-linking agent of the invention has better dimensional stability.

Description

Cross-linking agent
Technical field
The present invention relates to a kind of cross-linking agent, particularly to a kind of crosslinking including there is the polymer of amino Agent, and relate to the cross-linking agent of a kind of clay-polyurethane including having NCO.
Background technology
The purposes of epoxy resin (epoxy resins) is quite extensive, by different types of epoxy resin and crosslinking Agent carries out the product of cross-linking reaction formation and can apply to various field, and cross-linking agent can also decide cross-linking reaction The character of the product formed, such as: mechanicalness, resistance to acids and bases or impact resistance etc..
Such as: the substrate used by printed circuit board (PCB) (Printed wire board) is exactly by epoxy resin and crosslinking Obtained by agent is reacted.But, the poor dimensional stability of epoxy resin itself, thus cause being formed The poor dimensional stability of substrate and do not meet the industry requirement to printed circuit board (PCB), therefore there is a need to by Cross-linking agent promotes the dimensional stability of substrate.
In view of above-mentioned, improve cross-linking agent, so that cross-linking agent has preferably dimensional stability, then promote The effect of subsequent applications, is the problem that can break through again of this technical field person skilled.
Summary of the invention
The first object of the present invention is the cross-linking agent providing a kind of dimensional stability high.
Cross-linking agent of the present invention, comprises by including clay-polyurethane and two amine compounds with NCO First component of thing is through the polymer with amino obtained by the first polyreaction；This has isocyanates The clay-polyurethane of base is by including having the most dihydric clay-polyurethane and the first multicomponent isocyanate The second component of compound is through obtained by the second polyreaction, and this has the most dihydric clay-poly- Urethane is by including having dihydric clay, polyol compound and the second polyhydric isocyanate compound 3rd component is obtained through third polymerization reaction；Wherein, this has the most dihydric clay-polyurethane Weight average molecular weight scope be less than 2000, the molecular weight ranges of this polyol compound be 700 with Under, the molecular weight ranges of this second polyhydric isocyanate compound is less than 300.
The second object of the present invention is the cross-linking agent providing a kind of dimensional stability high.
Cross-linking agent of the present invention, comprises by including having the most dihydric clay-polyurethane and more than first yuan The second component of isocyanate compound is through having the viscous of NCO obtained by the second polyreaction Soil-polyurethane, and this have the most dihydric clay-polyurethane by include having dihydric clay, Polyol compound reacts made with the 3rd component of the second polyhydric isocyanate compound through third polymerization ?；Wherein, this weight average molecular weight with the most dihydric clay-polyurethane is less than 2000, The molecular weight of this polyol compound is less than 700, the molecular weight of this second polyhydric isocyanate compound It is less than 300.
Cross-linking agent of the present invention, the molal quantity of the NCO in this first polyhydric isocyanate compound, There is the ratio range of molal quantity of hydroxyl in the most dihydric clay-polyurethane for more than 1 with this.
Cross-linking agent of the present invention, the molal quantity of the NCO in this second polyhydric isocyanate compound, It is little with this ratio range with the total hydroxyl moles in dihydric clay and polyol compound In 1.
Cross-linking agent of the present invention, this diamine compound is selected from isophorone diamine, ethylenediamine, tetramethyl second Diamidogen, tetraethylethylenediamine or combinations thereof.
Cross-linking agent of the present invention, this polyol compound selected from ethylene glycol, propylene glycol, butanediol, 1,3- Butanediol, neopentyl glycol, polyether polyol, PEPA, polycarbonate polyol or their group Close.
Cross-linking agent of the present invention, this first polyhydric isocyanate compound selected from toluene di-isocyanate(TDI), two Phenyl methylidene group diisocyanate, hexamethylene diisocyanate, 4,4-dicyclohexylmethylene two isocyanide Acid esters, isophorone diisocyanate or combinations thereof.
Cross-linking agent of the present invention, this second polyhydric isocyanate compound selected from toluene di-isocyanate(TDI), two Phenyl methylidene group diisocyanate, hexamethylene diisocyanate, 4,4-dicyclohexylmethylene two isocyanide Acid esters, isophorone diisocyanate or combinations thereof.
Cross-linking agent of the present invention, this has dihydric clay by including clay and the quaternary ammonium salt shown in formula (I) 4th component is formed；
In formula (I), this R1And R2Represent C respectively1To C18Alkyl；X represents the season shown in maintenance formula (I) The electroneutral anion of ammonium salt.
The beneficial effects of the present invention is: this cross-linking agent has preferably dimensional stability, after then promoting The effect of continuous application.
Detailed description of the invention
Hereinafter will be described in detail with regard to present invention:
For being conducive to this polyol compound to insert this interlayer with dihydric clay, this polynary alcoholization The molecular weight ranges of compound is less than 700.
It is preferred that this polyol compound selected from ethylene glycol, propylene glycol, butanediol, 1,3 butylene glycol, Neopentyl glycol, polyether polyol, PEPA, polycarbonate polyol or combinations thereof.This gathers Ethoxylated polyhydric alcohol is such as but not limited to polypropylene glycol, polytetrahydrofuran diol, polytetramethylene ether glycol or poly- Propylene glycol-polytetrahydrofuran diol copolymer etc..More preferably, this polyol compound is selected from poly-carbonic acid Ester polyol, polyether polyol, PEPA, propylene glycol or combinations thereof.
For making this second polyhydric isocyanate compound promptly to react with this polyol compound, this is years old The molecular weight ranges of two polyhydric isocyanate compound is less than 300.
It is preferred that this second polyhydric isocyanate compound is selected from toluene di-isocyanate(TDI) (toluene Diisocyanate), MDI (methylenediphenyl diisocyanate), six Methylene diisocyanate (hexamethylene diisocyanate), 4,4-dicyclohexylmethylene two isocyanide Acid esters [4,4-methylene bis (isocyanatocyclohexane)], isophorone diisocyanate (isophorone diisocyanate) or combinations thereof.More preferably, this second multicomponent isocyanate chemical combination Thing is selected from 4,4-dicyclohexylmethylene diisocyanate, MDI, toluene Diisocyanate, isophorone diisocyanate or combinations thereof.It is preferred that with this polyol The gross weight of thing is 100 weight portions, and the usage amount scope of this second polyhydric isocyanate compound is 10 to 90 Weight portion.
It is preferred that the molal quantity of the NCO in this second multicomponent isocyanate, with this, there is dihydroxy The ratio range of the total hydroxyl moles in the clay of base and polyhydric alcohol is less than 1.
It is preferred that be 100 weight portions with the gross weight of this polyol compound, this has dihydric clay Usage amount scope be 5 to 90 weight portions.
It is preferred that this has dihydric clay by including the 4th group of the quaternary ammonium salt shown in clay and formula (I) Divide and formed；
In formula (I), this R1And R2Represent C respectively1To C18Alkyl；X represents the season shown in maintenance formula (I) The electroneutral anion of ammonium salt.
This clay is selected from montmorillonite, Muscovitum, Kaolin, Alumen, Vermiculitum (vermiculite), or they Combination.This montmorillonite is such as but not limited to sodium form montmorillonite or calcium type montmorillonite etc..This Muscovitum such as but It is not limited to sericite (sericite) etc..This Alumen is such as but not limited to silicon Alumen etc..
This quaternary ammonium salt is selected from two (hydrogenated tallow acyl ethyl) hydroxyethyl methyl ammonium methylsulfate ammonium (dihydrogenated tallowoylethyl hydroxyethylammonium methosulfate), dodecane Based quaternary ammonium salt trimerization hydrogen ammonium (quaternary lauryl tripolyoxyethylene ammonium Hydroxide), methyl Adeps Bovis seu Bubali two-2-ethoxy quaternary ammonium (methyl tallow bis-2-hydroxyethyl Quaternary ammonium), poly-(season distearyl amide ammonium chloride) [poly (quaternary distearyl Amido ammonium chloride)] or combinations thereof.It is preferred that be 100 weights with the total amount of this clay Amount part meter, the usage amount scope of the quaternary ammonium salt shown in this formula (I) is 2 to 40 weight portions.
This clay can be reacted or high temperature by ion exchange (ion exchange) with the quaternary ammonium salt shown in formula (I) Activation (activation) process forms this and has dihydric clay.For example, this clay is that sodium form is covered During de-soil, this sodium is present between cheating engaging layer, and the quaternary ammonium salt shown in this formula (I) passes through ion-exchange reactions, Sodium between displacement cheating engaging layer, and it is intercalation into the interlayer of sodium form montmorillonite, so that sodium form montmorillonite is upgraded And enlargement layer spacing.And for example, when this clay is Kaolin, it is placed under high temperature so that it is interlamellar spacing expands Greatly, meanwhile, introduce the quaternary ammonium salt shown in this formula (I), and be intercalation into kaolinic interlayer, so that Kaolin It is upgraded and enlargement layer spacing again.
3rd component also includes solvent and catalyst.This solvent is such as but not limited to N, N-dimethyl second Amide (N, N-dimethylacetamide), ethyl acetate (ethyl acetate), butyl acetate (butyl Acetate), methyl isopropyl ketone (methyl isopropyl ketone), acetone (acetone), isopropanol, isobutyl Alcohol, toluene, dimethylformamide (dimethylformamide), DAA (diacetone alcohol), Dimethyl sulfoxide (dimethyl sulfoxide) or butanone, above-mentioned solvent can be used alone or as a mixture.Many with this The gross weight of unit's alcoholic compound is 100 weight portions, and the usage amount scope of this solvent is 50 to 800 weight portions.Should Catalyst is such as but not limited to tetrabutyltin (tetra-n-butyltin), bismuth carboxylate (bismuth Carboxylate), pyrovinic acid bismuth (bismuth methansulfonate) or tin dilaurate dioctyl tin (dioctyltin dilaurate is called for short DOTL), above-mentioned catalyst can be used alone or as a mixture.Polynary with this The gross weight of alcoholic compound is 100 weight portions, and the usage amount scope of this catalyst is 0.01 to 0.5 weight portion.
It is preferred that the operating temperature range of this third polymerization reaction is 55 DEG C to 80 DEG C, operating time scope It it is 0.5 hour to 10 hours.
This end obtained by third polymerization is reacted has the weight of the clay-polyurethane of at least two hydroxyls Amount average molecular weight range is less than 2000, thus dispersibility is preferable.
It is preferred that this first polyhydric isocyanate compound is sub-selected from toluene di-isocyanate(TDI), diphenyl Methyl diisocyanate, hexamethylene diisocyanate, 4,4-dicyclohexylmethylene diisocyanate, Isophorone diisocyanate or combinations thereof.More preferably, this first polyhydric isocyanate compound choosing From in 4,4-dicyclohexylmethylene diisocyanate, isophorone diisocyanate, diphenylmethylene Diisocyanate, hexamethylene diisocyanate or combinations thereof.It is preferred that with this polyol The gross weight of thing is 100 weight portions, and the usage amount scope of this first polyhydric isocyanate compound is 10 to 100 Weight portion.
It is more than two for making this NCO number having in the clay-polyurethane of NCO, It is preferred that the molal quantity of the NCO in this first multicomponent isocyanate, with this, there is at least dihydroxy The ratio range of the molal quantity of the hydroxyl in the clay-polyurethane of base is more than 1.
This second component also includes solvent and catalyst.The kind of this solvent and catalyst be as it has been described above, Therefore repeat no more.It is 100 weight portions with the gross weight of this polyol compound, the usage amount scope of this solvent It is 50 to 800 weight portions.It is 100 weight portions with the gross weight of this polyol compound, the use of this catalyst Weight range is 0.01 to 0.5 weight portion.
It is preferred that the operating temperature range of this second polyreaction is 55 DEG C to 100 DEG C, operating time model Enclose is 0.5 hour to 10 hours.
It is preferred that this diamine compound is selected from isophorone diamine (isophorondiamine), ethylenediamine (ethylenediamine), tetramethylethylenediamine (tetramethylethylenediamine), tetraethylethylenediamine Or combinations thereof (tetraethylethylenediamine).It is preferred that with the gross weight of this polyol compound Being 100 weight portions, the usage amount scope of this diamine compound is 1 to 30 weight portion.
This first component also includes solvent and catalyst, the kind of this solvent and catalyst be as it has been described above, Therefore repeat no more.It is 100 weight portions with the gross weight of this polyol compound, the usage amount scope of this solvent It is 50 to 80 weight portions.It is 100 weight portions with the gross weight of this polyol compound, the use of this catalyst Weight range is 0.01 to 0.5 weight portion.
It is preferred that the operating temperature range of this first polyreaction is 40 DEG C to 60 DEG C, and operating time model Enclose is 0.5 hour to 5 hours.
This cross-linking agent is suitable as the crosslinking of epoxy resin because comprising this polymer with amino Agent, such as: this cross-linking agent and epoxy resin react and can prepare an epoxy resin base plate.This cross-linking agent has The advantage that dimensional stability is high, so that follow-up prepared epoxy resin base plate has dimensional stability height Advantage.
And this cross-linking agent is applicable to because comprising this clay-polyurethane with NCO as poly- The cross-linking agent of urethane, such as, can be applicable to the preparation of synthetic polyurethane leather.The dimensionally stable of this cross-linking agent Property high, so that follow-up prepared product has the advantage that dimensional stability is high.
The present invention will be described further with regard to following example, however, it should be noted that these embodiments are only For illustrating, and it is not necessarily to be construed as the restriction that the present invention implements.
[embodiment 1] cross-linking agent
After adding 35 grams of N,N-dimethylacetamide in a reactive tank, add 100 grams (0.2 moles) and gather Carbonate polyol (UH-50 that Ube Industries, Ltd (Ube Industries, Ltd) makes, weight average Molecular weight 500), the 4,4-dicyclohexyl methyl hydride diisocyanate of 38.4 grams (0.15 moles), 0.06 gram of four fourth Ji Xi, and 20 grams there is the dihydric clay C34-M30 of enamel frit makeing (China), carry out at 85 ± 5 DEG C Polyreaction 4 hours, makes 4, and 4-dicyclohexyl methyl hydride diisocyanate reacts complete completely, obtain having to Few dihydric clay-polyurethane (weight average molecular weight is 2,000).320 are added in this reactive tank Gram N,N-dimethylacetamide, and 30.7 grams of (0.12 moles) 4,4-dicyclohexyl methyl hydride diisocyanate, and At 60 ± 5 DEG C, carry out polyreaction 1 hour, obtain the clay-polyurethane with NCO.Connect , the temperature at this reactive tank is at 50 ± 5 DEG C, by the isophorone that total amount is 2.4 grams (0.014 moles) Diamidogen divides 2 to 3 times and adds in reactive tank, and carries out polyreaction 1 hour, confirms in this reactive tank Isocyanate-free base remains, and obtains the polymer with amino of 546.56 grams, is the crosslinking of embodiment 1 Agent.
[embodiment 2 to 5] cross-linking agent
To prepare the cross-linking agent of embodiment 2 to 5 with the identical flow process of embodiment 1, difference is according to table 1, Change the consumption of each raw material.
[embodiment 6] cross-linking agent
After adding 35 grams of N,N-dimethylacetamide in reactive tank, add 100 grams of (0.2 mole) poly-carbonic acid Ester polyol (UH-50 that Ube Industries, Ltd (Ube Industries, Ltd) makes, weight averaged molecular Amount 500), the 4 of 38.4 grams (0.15 moles), 4-dicyclohexyl methyl hydride diisocyanate, 0.06 gram of tetrabutyltin, And 20 grams there is the dihydric clay C34-M30 of enamel frit makeing (China), at 85 ± 5 DEG C, carry out polymerization anti- Answering 4 hours, make 4,4-dicyclohexyl methyl hydride diisocyanate reacts complete completely, obtains having at least dihydroxy The clay-polyurethane (weight average molecular weight is 2000) of base.320 grams of N, N-are added in this reactive tank Dimethyl acetylamide and 30.7 grams of (0.12 moles) 4,4-dicyclohexyl methyl hydride diisocyanate, and in 60 ± 5 DEG C Under carry out polyreaction 1 hour, obtain the clay-polyurethane with NCO of 544.16 grams, i.e. Cross-linking agent for embodiment 6.
[embodiment 7 to 8] cross-linking agent
To prepare the cross-linking agent of embodiment 7 to 8 with the identical flow process of embodiment 6, difference is according to table 2, Change the consumption of each raw material.
[comparative example 1] composite organic-inorganic material
Refering to the Organic-inorganic composite material disclosed in concrete example 1 in Taiwan Patent publication number 20130034255 Material.
[application examples 1] epoxy resin base plate
By embodiment 1 cross-linking agent of 5 grams and the epoxy resin (NPCN-704 of Nan Ya Plastics company) of 95 grams Stir 5 minutes with the rotating speed of 1500rpm, make both mix and react, the epoxy resin of the example that is applied 1 Substrate.
[application examples 2 to 5 and compare application examples 1] epoxy resin base plate
With flow process application and preparation example 2 to 5 identical with application examples 1 and compare application examples 1, difference be according to Table 1, uses different cross-linking agent.
[application examples 6] synthetic polyurethane leather
By embodiment 6 cross-linking agent of 10 grams and polyurethane (Fu Yu Advanced Materials Corp. of 100 grams The 5505Y of system) stir 5 minutes with the rotating speed of 1500rpm, make both mix and react, be applied example 6 Synthetic polyurethane leather.
[application examples 7 to 8 and compare application examples 2] synthetic polyurethane leather
With flow process application and preparation example 7 to 8 identical with application examples 6 and compare application examples 2, difference be according to Table 2, uses different cross-linking agent.
[detection project]
1. thermal coefficient of expansion (%):
Respectively by application examples 1 to 8 and compare application examples 1 to 2 and make standard film size, use thermal coefficient of expansion Instrument (label: Yaofu Precision Science & Technology Co., Ltd.；Model: UF-COE-1000) according to ASTM E831 Standard maneuver, measures thermal coefficient of expansion.The numerical value of thermal coefficient of expansion is the least, represents the effect of dimensional stability Fruit is better.
2. aqueous vapor penetrance aberration rate (%):
Use aqueous vapor penetrance analyzer (label: Systech Instruments Ltd；Model LYSSY L80-5000), (Water Vapor Transmission Rate is called for short WVTR to measure vapor transmission rate； Unit: g/m2-sky).With Study On O-cresol Epoxy Resin (label: Nan Ya Plastics company；Model: NPCN-704) make standard film to be placed in sample cell, sample cell will be separated out two spaces, wherein One space as hothouse, another space as moist room and temperature and humidity are controlled respectively at 25 DEG C and Relative humidity 40%.Now, the aqueous vapor in moist room can gradually diffuse to hothouse, and standard is crossed in break-through Sheet, the aqueous vapor of break-through can mix with dry original with hothouse, be brought to infrared induction together Device, then measures the infrared energy data of gained, and converts thereof into electronic signal, then calculate The vapor transmission rate (B1) of standard film.Respectively by application examples 1 to 5 and compare application examples 1 and make standard film Size, and measure according to aforesaid way, obtain vapor transmission rate (B2).Vapor transmission rate makes a variation The calculation of rate: | (B1-B2) ÷ B1 × 100%.The numerical value of this vapor transmission rate aberration rate is more Greatly, then moisture obstruction is represented better.
3. interlamellar spacing (nm):
Use X-ray powder diffraction instrument (label: West Germany BRUKER；Model: D8AXRD), measure real Execute interlamellar spacing (d-spacing, the list of the cross-linking agent of example 1 to 8 and the composite organic-inorganic material of comparative example 1 Position: nm).The numerical value of interlamellar spacing is the biggest, then represent dispersibility effect better.
4. softening point temperature (DEG C)
Respectively by application examples 6 to 8 and compare application examples 2 and make the test piece of 20mm × 60mm, and note down test piece Thickness.Test piece being put in baking oven, one end is fixed, and the other end is with transverse section stress as 450g/cm2 Strength, and heat up with 2 DEG C/min programming rate, test piece be pulled to temperature during fracture, be Softening point temperature.
Table 1
Note: "---" indicates without using or without measuring.
Table 2
From the experimental result of table 1, with application examples 1 to 5 ring obtained by the cross-linking agent of embodiment 1 to 5 Epoxy resins substrate has relatively low thermal coefficient of expansion, represents that the size of application examples 1 to 5 epoxy resin base plate is steady Qualitative preferably.And use comparison application examples 1 asphalt mixtures modified by epoxy resin obtained by comparative example 1 composite organic-inorganic material The thermal coefficient of expansion of aliphatic radical plate is higher, represents and compares the dimensional stability of application examples 1 epoxy resin base plate relatively Difference.
From the experimental result of table 2, have with the application examples 6 to 8 obtained by the cross-linking agent of embodiment 6 to 8 Having relatively low thermal coefficient of expansion, the dimensional stability representing application examples 6 to 8 is preferable.And use comparative example 1 The thermal coefficient of expansion of the comparison application examples 2 obtained by composite organic-inorganic material is higher, represents and compares application The dimensional stability of example 2 is poor.
In sum, cross-linking agent of the present invention has the advantage that dimensional stability is high, then can promote follow-up answering Effect, therefore really can reach the purpose of the present invention.
Simply the above, for presently preferred embodiments of the present invention, real when not limiting the present invention with this The scope executed, say, that generally according to scope of the invention as claimed and invention description content made simple Equivalence change with modify, the most still remain within the scope of the patent.

Claims (10)

1. a cross-linking agent, it is characterised in that it comprises by the clay including having NCO-poly- First component of urethane and diamine compound is through the polymer with amino obtained by the first polyreaction； The described clay-polyurethane with NCO by include having the most dihydric clay-polyurethane with The second component of the first polyhydric isocyanate compound through obtained by the second polyreaction, and described in have to Few dihydric clay-polyurethane is by including having dihydric clay, polyol compound and more than second 3rd component of unit's isocyanate compound is obtained through third polymerization reaction；Wherein, have at least described in The weight average molecular weight scope of dihydric clay-polyurethane is less than 2000, described polyol The molecular weight ranges of thing is less than 700, and the molecular weight ranges of described second polyhydric isocyanate compound is Less than 300.
Cross-linking agent the most according to claim 1, it is characterised in that described first multicomponent isocyanate The molal quantity of the NCO in compound, has in the most dihydric clay-polyurethane with described The ratio range of molal quantity of hydroxyl be more than 1.
Cross-linking agent the most according to claim 1, it is characterised in that described second multicomponent isocyanate The molal quantity of the NCO in compound, has dihydric clay and described polynary alcoholization with described The ratio range of the total hydroxyl moles in compound is less than 1.
Cross-linking agent the most according to claim 1, it is characterised in that described diamine compound is selected from Isophorone diamine, ethylenediamine, tetramethylethylenediamine, tetraethylethylenediamine or combinations thereof.
Cross-linking agent the most according to claim 1, it is characterised in that described polyol compound is selected from Many in ethylene glycol, propylene glycol, butanediol, 1,3 butylene glycol, neopentyl glycol, polyether polyol, polyester Unit's alcohol, polycarbonate polyol or combinations thereof.
Cross-linking agent the most according to claim 1, it is characterised in that described first multicomponent isocyanate Compound is selected from toluene di-isocyanate(TDI), MDI, hexa-methylene two isocyanide Acid esters, 4,4-dicyclohexylmethylene diisocyanate, isophorone diisocyanate or combinations thereof.
Cross-linking agent the most according to claim 1, it is characterised in that described second multicomponent isocyanate Compound is selected from toluene di-isocyanate(TDI), MDI, hexa-methylene two isocyanide Acid esters, 4,4-dicyclohexylmethylene diisocyanate, isophorone diisocyanate or combinations thereof.
Cross-linking agent the most according to claim 1, it is characterised in that described in there is dihydric clay By including that the clay the 4th component with the quaternary ammonium salt shown in formula (I) is formed；
In formula (I), described R1And R2Represent C respectively1To C18Alkyl；X represents shown in maintenance formula (I) The electroneutral anion of quaternary ammonium salt.
9. a cross-linking agent, it is characterised in that it comprises by including having the most dihydric clay-poly- The second component of urethane and the first polyhydric isocyanate compound is through having obtained by the second polyreaction The clay-polyurethane of NCO；Described have the most dihydric clay-polyurethane by including having 3rd component of dihydric clay, polyol compound and the second polyhydric isocyanate compound is through the 3rd Obtained by polyreaction；Wherein, the weight average described in the most dihydric clay-polyurethane divides Son amount be less than 2000, the molecular weight of described polyol compound is less than 700, described more than second yuan different The molecular weight of cyanate esters is less than 300.
Cross-linking agent the most according to claim 9, it is characterised in that described first multicomponent isocyanate The molal quantity of the NCO in compound, has in the most dihydric clay-polyurethane with described The ratio range of molal quantity of hydroxyl be more than 1.
CN201510565568.2A 2015-05-01 2015-09-08 crosslinking agent Pending CN106084178A (en)

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CN1375524A (en) * 2001-03-21 2002-10-23 中国科学院化学研究所 Nanometer montmorillonoid-containing composite material and its prepn.
CN102850510A (en) * 2011-06-27 2013-01-02 永捷高分子工业股份有限公司 Organic-inorganic composite material and method for producing same

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US6887931B2 (en) * 2001-10-23 2005-05-03 Ashland Inc. Thermosetting inorganic clay nanodispersions and their use
EP2274254B1 (en) * 2008-05-06 2016-09-28 Huntsman International LLC Clay-isocyanate nanodispersions and polyurethane nanocomposite produced therewith

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Publication number Priority date Publication date Assignee Title
CN1374346A (en) * 2001-03-14 2002-10-16 中国科学院化学研究所 Compound containing nano montmorillonoid and its prepn
CN1375524A (en) * 2001-03-21 2002-10-23 中国科学院化学研究所 Nanometer montmorillonoid-containing composite material and its prepn.
CN102850510A (en) * 2011-06-27 2013-01-02 永捷高分子工业股份有限公司 Organic-inorganic composite material and method for producing same

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Application publication date: 20161109