CN106675488A - Isocyanate adhesive and method for preparing multilayer polyurethane structural composite by using same - Google Patents
Isocyanate adhesive and method for preparing multilayer polyurethane structural composite by using same Download PDFInfo
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- CN106675488A CN106675488A CN201510759860.8A CN201510759860A CN106675488A CN 106675488 A CN106675488 A CN 106675488A CN 201510759860 A CN201510759860 A CN 201510759860A CN 106675488 A CN106675488 A CN 106675488A
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- isocyanate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- 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
- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
- B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
-
- 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
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/08—Polyurethanes from polyethers
-
- 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
- B32B2250/00—Layers arrangement
- B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
-
- 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
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/10—Inorganic fibres
- B32B2262/101—Glass fibres
-
- 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
- B32B2605/00—Vehicles
- B32B2605/003—Interior finishings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses an isocyanate adhesive. The adhesive comprises: A, an isocyanate component; B, a composite catalyst aqueous solution. The composite catalyst comprises an amine-containing organic compound and an aminocarboxylate stabilizer; aminocarboxylate is added, so that insoluble substances generated by an amine catalyst in water can be inhibited; water spraying equipment is not blocked in the application process; the curing speed of the isocyanate adhesive can be properly adjusted by changing the concentration of the catalyst; the operation is convenient. The invention also discloses a method for preparing a multilayer polyurethane structural composite by using the isocyanate adhesive. The prepared multilayer polyurethane structural composite can be applied to interior components and can be particularly applied to automobile ceiling roof components.
Description
Technical field
The present invention relates to a kind of isocyanate adhesive and by its prepare polyurethane multilayer structures composite,
In particular for the preparation method of the polyurethane multilayer structures composite of automobile component,.
Background technology
In general, soft polyurethane foam is mainly used in field of furniture, with foamed open cell, softness, extension
The characteristic such as rate is higher；Hard polyurethane foam is mainly used in the insulation material of the aspects such as building, household electrical appliance, bubble
Foam closed pore, the rigidly characteristic such as larger, more crisp.
Automobile ceiling field, the polyurethane foam for using between soft bubble and between hard bubbling, therefore, referred to as half
Hard polyurethane foams.Preparing polyurethane automobile top generally has two kinds of techniques：One kind is dry method, another kind of
It is wet method.From for the theory of macromolecular material, for the semi-rigid thermoplastic urethane foam of automobile ceiling
Need with appropriate glass transition temperature so that the hot formability that foam had both had, the summer is avoided again
Season, hot weather caused the recovery of foam shape, caused the deformation of roof.
In the evolution of polyurethane roof, dry process starting is relatively early, and wet processing is in development in recent years
Comparatively fast.Both compare, and dry process is pre-composite through sheet material, roof is molded two steps and completes, and efficiency is inadequate
It is high.Wet processing efficiency is higher, and compound, one step of shaping is completed.
Using method comprising adhesive in wet polyurethane automobile calash preparation method commonly used in the art,
First catalyst is added in isocyanate adhesive, then adhesive roller is coated in into the side of polyurethane foam sheet material
Or both sides, then water spray, cover glass and non-woven fabrics, it is compressing to be placed on mould high temperature, although adopting
With the isocyanate adhesive less sensitive to moisture, but still suffer from during use adhesive viscosity increase,
Bonding rubber roll, also resulting in resin added can not be controlled；Another kind of technical scheme is in polyurethane foam sheet
Adhesive of the material roller coat without catalyst, sprays again the aqueous solution containing catalyst and enters in later stage preparation process
Row solidification, but conventional catalyst is higher to the quality requirement of water, and wadding such as can be produced in city tap-water
Shape thing or precipitation, can increase the difficulty of material preparation process and affect the quality of product, for example, these
Amines catalyst, specific such as triethylene diamine, dimethylaminoethyl ether are included in custom catalystses.
Some technical schemes are prior art discloses, such as CN103921504 discloses a kind of roof preparation technology
Polyurethane adhesive, hot melt adhesive film is replaced not to have foaming process using hot melt adhesive film, adhesive property is compared with polyurethane
Moisturecuring glue is poor, and CN104031596A discloses a kind of low forming temperature water-based polyurethane adhesive and its preparation
Method, the adhesive does not contain organic solvent, low VOC, but its preparation process and on automobile calash
Using more complicated, but these technical schemes can not solve these problems that presently, there are.
Accordingly, it would be desirable to a kind of preparation method of new automobile calash polyurethane multilayer structures composite is developed,
To solve problems of the prior art, while optimizing the processing technology that current industrial production is commonly used.
The content of the invention
The purpose of the present invention aims to provide a kind of isocyanate adhesive.
Present invention also offers a kind of preparation method of multilayer polyurethane structural composite material, makes in preparation process
Use adhesive of the present invention.
In order to realize above goal of the invention, the technical solution used in the present invention is as follows：
A kind of isocyanate adhesive, comprising following components：
A. isocyanate component；
B. the composite catalyst aqueous solution；
Wherein, the composite catalyst includes amine organic compound and amino carboxylic acid salt stabilizing agent.
Component A of the present invention is 60-120 with the weight ratio of B component:10-50；Preferably, institute of the present invention
When stating isocyanate adhesive for preparing polyurethane multilayer structures composite, the weight of component A and B component
Amount is than being 70-100:20-30.
In isocyanate adhesive of the present invention, the component A is including but not limited to diphenyl methane two
In isocyanates, poly methylene poly phenyl poly isocyanate, Isocyanate prepolymers body one or two or it is many
Kind, preferred poly methylene poly phenyl poly isocyanate and/or Isocyanate prepolymers body, more preferably polymethylene is more
Polyphenyl polyisocyanate.
In the present invention, the NCO content of the component A is 29.5-32.1wt%, and the viscosity at 25 DEG C is
150-250mPas, preferred 180-230mPas.
In isocyanate adhesive of the present invention, poly methylene poly phenyl poly isocyanate described in component A
By the material composition for meeting following formulas for one or more：
Wherein, m for 0-6 integer, the integer of preferred 1-4.
In the isocyanate adhesive of the present invention, methyl diphenylene diisocyanate described in component A is 2,2'-
Methyl diphenylene diisocyanate, 2,4'- methyl diphenylene diisocyanates and 4,4'- diphenyl methane two are different
One or two or three kinds in cyanate, it is preferable that 4,4'- in the methyl diphenylene diisocyanate
Methyl diphenylene diisocyanate content is 90-100wt%, and 2,2'- methyl diphenylene diisocyanate contents are
0-10wt%, 2,4'- methyl diphenylene diisocyanate contents are 0-10wt%, with the isocyanide of diphenyl methane two
The gross weight meter of acid esters.
In the present invention, the Isocyanate prepolymers body is that isocyanates is prepared from PPG reaction,
Can also be commercially available prod, the NCO content of the Isocyanate prepolymers body is selected from, but not limited to, 21-25wt%,
It is preferred that 22-23.5wt%.
In the present invention, described PPG can be by propane diols, glycerine and trimethylolpropane
Plant or two or more startings, by obtaining with expoxy propane and/or ethylene oxide polymerization, the polyether polyols
The hydroxyl value of alcohol is 24-168mgKOH/g；Preferably, the PPG is initial by glycerine, by epoxy
Propane polymerization is obtained, and hydroxyl value is 30-58mgKOH/g.
In Isocyanate prepolymers production procedure of the present invention, participate in reaction isocyanates be selected from but not
It is limited to poly methylene poly phenyl poly isocyanate of the present invention and/or methyl diphenylene diisocyanate.
In the present invention, during the isocyanates prepares Isocyanate prepolymers body with PPG reaction,
Isocyanates is 85-98 with the weight ratio of PPG:The preferred 90-95 of 2-15:5-10；The prepolymerization reaction
It is to carry out under the protection of inert gas, the inert gas is preferably nitrogen, reaction temperature is 70-100 DEG C,
It is preferred that 75-80 DEG C, course of reaction continues 2.5-3 hours.
In the present invention, the isocyanates reacts the preparation side to form Isocyanate prepolymers body with PPG
Method within restrictive condition of the present invention, join by NM concrete operations condition of the invention, equipment, reaction
Number etc., can be realized using the method that those skilled in the art commonly use.
In the isocyanate adhesive of the present invention, urge comprising compound in the B component composite catalyst aqueous solution
Agent and water, the concentration of composite catalyst is 2-8wt%, preferably 3-5wt%, with the gross weight of B component
Meter.
The weight ratio of amine organic compound and amino carboxylic acid salt stabilizing agent is in B component of the present invention
100:0.5-3, preferably 100:1-2.
In composite catalyst aqueous solution B component of the present invention, the amino carboxylic acid salt stabilizing agent has such as
Lower structure：
Wherein, M1、M2、M3And M4It is identical or different, separately represent K+、Na+、Li+Or H+, preferably K+、Na+Or H+, more preferably Na+Or H+；Metal in the amino carboxylic acid molecules of salt from
Subnumber >=H+Number；N is 0～5 integer, preferably 0～3 integer.
As preferred scheme, in the present invention, preferred amino carboxylic acid salt stabilizing agent be aminotriacetic acid trisodium,
One kind or two in tetrasodium ethylenediamine tetraacetate, disodium ethylene diamine tetraacetate and the sodium of diethylene triamine pentacetic acid (DTPA) five
Plant or various.
Amine organic compound of the present invention include but is not limited to triethylene diamine, dimethylaminoethyl ether,
N,N-Dibenzylamine, N, N- dimethyl cyclohexyl amines, N-ethylmorpholine, N-methyldicyclohexylamine, pentamethyl
One or two or more in diethylenetriamine, triethylamine and dimethylethanolamine etc., preferred triethylene two
One or two or more in amine, dimethylaminoethyl ether and N,N-Dibenzylamine.
Used as further explanation and explanation, component A is reacted with water in isocyanate adhesive of the present invention
Bonding effect is played after solidification, hardening time is longer in the case of without catalyst, it is impossible to meet stripper
Skill is particularly applied to the needs of fast demoulding in roof preparation technology during automobile calash.Skill commonly used in the art
Art be by adding catalyst in water to accelerate the curing rate of adhesive, but due to water in (as originally
Water etc.) usually contain plurality of impurity ions, such as Ca in water2+、Mg2+Metal ion may be urged with amine
Agent forms indissoluble thing, and sediment is separated out from water；Therefore, easily occur after amines catalyst is added in water
Flocculent undissolved substance, thus blocking sprinkler, affect being normally carried out for roof preparation technology.
In the isocyanate adhesive of the present invention, the composite catalyst is very high for the adaptability of water, when matching somebody with somebody
It is of the present invention when during the composite catalyst aqueous solution processed using the water containing foreign ion (such as running water)
Composite catalyst will not produce precipitation or cotton-shaped impurity in water, it is adaptable to industrial production, can play reduction
The effect of cost.
The present invention also provides a kind of preparation method of polyurethane multilayer structures composite, and preparation process includes：
A. component A of the present invention is coated in the both sides of reinforcing material E；
B. in the side of polyurethane foam, repeat to implement following operation p time：Cover the enhancing of coating component A
Material E, and the outer surface in reinforcing material E sprays B component；
C. in the opposite side of polyurethane foam described in step b, repeat to implement following operation q time：Cover coating
The reinforcing material E of component A, and the outer surface in reinforcing material E sprays B component；Obtain MULTILAYER COMPOSITE
Structure；
The upper and lower surface of the multi-layer compound structure for d. obtaining in step c is covered each by one layer of reinforcing material F,
Form multilayer composite；
E. the multilayer composite for step d being obtained is compressing, obtains polyurethane multilayer structures composite；
Wherein, p and q can be the same or different, and be separately the integer of 1-5, preferred 1-3's
Integer.
In the preparation method of polyurethane multilayer structures composite of the present invention, the raw material includes polyurethane
Foam, reinforcing material E, reinforcing material F and the isocyanates comprising component A and B component of the present invention
Adhesive.
In preparation method of the present invention, the consumption of component A is 60-120g/m2, preferably 70-100g/m2,
The consumption of B component is 10-50g/m2, preferably 20-30g/m2。
In the preparation method of polyurethane multilayer structures composite of the present invention, described reinforcing material E and enhancing
Material F can be with identical, it is also possible to different, can including but not limited to cover thermoplastic hard or semi-hard polyurethane
The conventional reinforcing material of foam sheet.Used as preferred scheme, the reinforcing material F is non-woven fabrics, preferably
Automobile calash non-woven fabrics；The reinforcing material E is fabric, preferably Chopped Strand Mat, is more preferably combined
The Chopped Strand Mat of the standard of GB/T17470-2007 defineds, further preferred glass is uniformly dispersed, rigidity is good,
The special Chopped Strand Mat of automotive trim of any surface finish.
In the preparation method of polyurethane multilayer structures composite of the present invention, the polyurethane foam is thermoplasticity
Hard or semi-hard polyurethane foam sheet, preferred thermoplastic semi-hard polyurethane foam sheet is further excellent
Choosing, the density of described thermoplasticity semi-hard polyurethane foam sheet is 23～32kg/m3, elongation percentage ＞ 15%,
Tensile strength ＞ 150KPa, thickness 6-8mm；Certainly the polyurethane foam is not limited to these restrictions,
Polyurethane foam commonly used in this field also can be applied in the present invention, such as disclosed in CN102174166
Thermoplasticity semi-hard polyurethane foam.
In the present invention, used as most preferred scheme, the polyurethane foam is thermoplasticity semi-hard polyurethane bubble
Foam sheet material, reinforcing material E is Chopped Strand Mat, and reinforcing material F is non-woven fabrics, and it is 1 that p is 1, q, described poly-
Urethane layer composite material preparation process includes：
A. component A of the present invention is coated in the both sides of Chopped Strand Mat；
B., the Chopped Strand Mat of the coating component A is covered in the both sides of thermoplasticity semi-hard polyurethane foam sheet,
And the outer surface in Chopped Strand Mat sprays B component of the present invention, obtains three-layer composite structure；
C. non-woven fabrics is covered in the both sides of three-layer composite structure, forms five layers of complex；
D. it is five layers of complex is compressing in a mold, obtain polyurethane five-layer structure composite.
Multilayer composite of the present invention is compressing in a mold, and mold temperature is 90-130 DEG C, preferably
For 100-120 DEG C；Press time be the 20-40 seconds, the preferred 25-30 seconds；Pressing process of the present invention also may be used
Other the conventional pressing process adopted using those skilled in the art.
Needs be explained further and illustrate, in preparation method of the present invention without restriction technique,
The factors such as equipment, parameter, can be applied to the technical scheme that those skilled in the art commonly use in the present invention,
And reach the purpose of the present invention；The coating of such as isocyanate component A uses method of roller coat etc..
Isocyanate component A roller coat of the present invention is operationally interior to ignore air on glass
The impact of middle moisture, resin added can be controlled accurately；Additionally, the composite catalyst will not in urban water
Sediment is produced, the composite catalyst aqueous solution will not block sprinkler.
Application of the polyurethane multilayer structures composite prepared by the present invention in top, preferably water, land,
Application in the top part of air transportation means, the more preferably application in the top part of automobile.
The beneficial effects of the present invention is：The aminocarboxylic introduced in the composite catalyst aqueous solution that the present invention is adopted
Hydrochlorate stabilizer, in polyurethane multilayer structures composite material is prepared, can effectively suppress to be precipitated in water
The generation of thing, eliminates the product quality problem caused due to the blocking of aqueous catalyst solution spray appliance, improves
Production efficiency.Simultaneously as the application of composite catalyst of the present invention, can include in isocyanate component
A small amount of catalyst, preferably not comprising catalyst, this isocyanate component for not containing catalyst is coated
Cheng Zhong, will not be affected by moisture in air and be solidified, and proterties is stablized in coating procedure so that be coated in
Glue amount on reinforcing material is stablized, and stable glue amount causes the composite different parts prepared to keep
Homogeneous outward appearance and physical property.
Specific embodiment
The present invention is further described below by embodiment, but the invention is not limited in these realities
Apply example.
Viscosity determining procedure：At 25 DEG C, tested with NDJ-7 types rotation viscometer, Shanghai balance equipment factory.
NCO testing standards：Using dibutyl amine method, according to GB12009.4-89
Aminotriacetic acid trisodium purity 95wt%
Tetrasodium ethylenediamine tetraacetate purity 95wt%；
Disodium ethylene diamine tetraacetate purity 95wt%；
Sodium purity 95wt% of diethylene triamine pentacetic acid (DTPA) five；
PPG 1：Glycerine starting, degree of functionality is 3, and Polymerization of Propylene Oxide, hydroxyl value is 56mgKOH/g.
PPG 2：Glycerine starting, degree of functionality is 3, ethylene oxide-capped, ethylene oxide content 15wt%,
Hydroxyl value is 51mgKOH/g；
Polymeric MDI：PM200, Wanhua Chemical Group Co., Ltd.；
Embodiment 1
Isocyanate component A1：PM200, viscosity 200mPaS (25 DEG C), NCO content 31%.
Composite catalyst aqueous solution B1：Concentration is 3wt%, and composite catalyst is 100 by weight ratio:The two of 2
Methylaminoethyl ether is constituted with aminotriacetic acid trisodium.
In the coated on both sides isocyanate component A1 of Chopped Strand Mat, the both sides of polyurethane foam, shape are respectively overlay in
Into three-decker, composite catalyst aqueous solution B1 is sprayed in three-decker both side surface, and covers non-woven fabrics,
Suppress in 130 DEG C of mould 28 seconds and be molded, obtain polyurethane five-layer structure composite.
Wherein, the consumption of isocyanate component A1 is 60g/m2, the consumption of composite catalyst aqueous solution B1 is
50g/m2。
Produce without precipitation during composite catalyst aqueous solution B1 sprinklings in embodiment, isocyanate component A1
Coating uniform ground, composite flat appearance is good.
Embodiment 2
Isocyanate component A2：PM200, viscosity 200mPaS (25 DEG C), NCO content 31%.
Composite catalyst aqueous solution B2：Concentration 8wt%, composite catalyst is 100 by weight ratio:The two of 0.5
Methylaminoethyl ether is constituted with aminotriacetic acid trisodium.
In the coated on both sides isocyanate component A2 of Chopped Strand Mat, the both sides of polyurethane foam, shape are respectively overlay in
Into three-decker, composite catalyst aqueous solution B2 is sprayed in three-decker both side surface, and covers non-woven fabrics,
Suppress in 90 DEG C of mould 40 seconds and be molded, obtain polyurethane five-layer structure composite.
Wherein, the consumption of isocyanate component A2 is 90g/m2, the consumption of composite catalyst aqueous solution B2 is
10g/m2。
Produce without precipitation during composite catalyst aqueous solution B2 sprinklings in embodiment, isocyanate component A2
Coating uniform ground, composite flat appearance is good.
Embodiment 3
Isocyanate component A3：The PPG 1 of PM200 and 5 part of 95 parts by weight react and
Into, viscosity 220mPaS (25 DEG C), NCO content 30.2%.
Composite catalyst aqueous solution B3：Concentration 5wt%, composite catalyst is 100 by weight ratio:1 three second
Alkene diamines is constituted with tetrasodium ethylenediamine tetraacetate.
In the coated on both sides isocyanate component A3 of Chopped Strand Mat, the both sides of polyurethane foam, shape are respectively overlay in
Into three-decker, composite catalyst aqueous solution B3 is sprayed in three-decker both side surface, and covers non-woven fabrics,
Suppress in 110 DEG C of mould 20 seconds and be molded, obtain polyurethane five-layer structure composite.
Wherein, the consumption of isocyanate component A3 is 70g/m2, the consumption of composite catalyst aqueous solution B3 is
20g/m2。
Produce without precipitation during composite catalyst aqueous solution B3 sprinklings in embodiment, isocyanate component A3
Coating uniform ground, composite flat appearance is good.
Embodiment 4
Isocyanate component A4：95 parts by weight of PM200 and 5 part of PPG 1 reaction is formed,
Viscosity 220mPaS (25 DEG C), NCO content 30.2%.
Composite catalyst aqueous solution B4：Dimorpholine ethylether in composite catalyst：(disodium ethylene diamine tetraacetate and
Tetrasodium ethylenediamine tetraacetate)=100:3 (weight ratios), the concentration of composite catalyst aqueous solution B4 is 2wt%.
In the coated on both sides isocyanate component A4 of Chopped Strand Mat, the both sides of polyurethane foam, shape are respectively overlay in
Into three-decker, composite catalyst aqueous solution B4 is sprayed in three-decker both side surface, then in three-decker
Both sides are covered each by Chopped Strand Mat, form five-layer structure, and in five-layer structure both side surface composite catalyst water is sprayed
Solution B 4, and non-woven fabrics is covered, suppress in 120 DEG C of mould 30 seconds and be molded, obtain seven layers of knot of polyurethane
Structure composite.
Wherein, the consumption of isocyanate component A4 is 100g/m2, the consumption of composite catalyst aqueous solution B4
For 30g/m2。
Produce without precipitation during composite catalyst aqueous solution B4 sprinklings in embodiment, isocyanate component A4
Coating uniform ground, composite flat appearance is good.
Embodiment 5
Isocyanate component A5：90 parts by weight of PM200 and 10 part of PPG 2 reaction is formed,
Viscosity 230mPaS (25 DEG C), NCO content 29.8%.
Composite catalyst aqueous solution B5：Composite catalyst is 100 by weight ratio:1.5 dimorpholine ethylether with
The sodium of diethylene triamine pentacetic acid (DTPA) five is constituted, and accounts for the 4wt% of composite catalyst aqueous solution B5 gross weights.
In the coated on both sides isocyanate component A5 of Chopped Strand Mat, the both sides of polyurethane foam, shape are respectively overlay in
Into three-decker, composite catalyst aqueous solution B5 is sprayed in three-decker both side surface, then in three-decker
Both sides are covered each by Chopped Strand Mat, form five-layer structure, and in five-layer structure both side surface composite catalyst water is sprayed
Solution B 5, and non-woven fabrics is covered, suppress in 130 DEG C of mould 25 seconds and be molded, obtain seven layers of knot of polyurethane
Structure composite.
Wherein, the consumption of isocyanate component A5 is 120g/m2, the consumption of composite catalyst aqueous solution B5
For 40g/m2。
Produce without precipitation during composite catalyst aqueous solution B5 sprinklings in embodiment, isocyanate component A5
Coating uniform ground, composite flat appearance is good.
Comparative example 1
Isocyanate component：PM200, viscosity 200mPaS (25 DEG C), NCO content 31%.
Catalyst is the aqueous solution that dimethylaminoethyl ether content is 3wt%.
In the coated on both sides isocyanate component A1 of Chopped Strand Mat, the both sides of polyurethane foam, shape are respectively overlay in
Into three-decker, composite catalyst aqueous solution B1 is sprayed in three-decker both side surface, and covers non-woven fabrics,
Suppress in 130 DEG C of mould 28 seconds and be molded, obtain polyurethane five-layer structure composite.
Wherein, the consumption of isocyanate component A1 is 60g/m2, the consumption of composite catalyst aqueous solution B1 is
50g/m2。
Because there is blocking in the equipment for spraying aqueous catalyst solution, it is impossible to normal continuous production.
Claims (11)
1. a kind of isocyanate adhesive, comprising following components：
A. isocyanate component；
B. the composite catalyst aqueous solution；
Wherein, the composite catalyst includes amine organic compound and amino carboxylic acid salt stabilizing agent.
2. isocyanate adhesive according to claim 1, it is characterised in that the aminocarboxylate is steady
Determine agent and there is following structure：
Wherein, M1、M2、M3And M4It is identical or different, separately represent K+、Na+、Li+Or H+, preferably K+、Na+Or H+, more preferably Na+Or H+；Metal in the amino carboxylic acid molecules of salt from
Subnumber >=H+Number；N is 0～5 integer, preferably 0～3 integer；
Preferred amino carboxylic acid salt stabilizing agent is aminotriacetic acid trisodium, tetrasodium ethylenediamine tetraacetate, ethylenediamine
One or two or more in tetraacethyl disodium and the sodium of diethylene triamine pentacetic acid (DTPA) five.
3. isocyanate adhesive according to claim 1 and 2, it is characterised in that the amine is organic
The weight ratio of compound and amino carboxylic acid salt stabilizing agent is 100:0.5-3, preferably 100:1-2.
4. the isocyanate adhesive according to claim 1 or 3, it is characterised in that the amine is organic
Compound be triethylene diamine, dimethylaminoethyl ether, N,N-Dibenzylamine, N, N- dimethyl cyclohexyl amines,
In N-ethylmorpholine, N-methyldicyclohexylamine, pentamethyl-diethylenetriamine, triethylamine and dimethylethanolamine
One or two or more, in preferred triethylene diamine, dimethylaminoethyl ether and N,N-Dibenzylamine
One or two or more.
5. the isocyanate adhesive according to any one of claim 1-4, it is characterised in that the A
Component is 60-120 with the weight ratio of B component:10-50, preferred 70-100:20-30.
6. isocyanate adhesive according to claim 1, it is characterised in that the composite catalyst water
The concentration of solution is 2-8wt%, preferred 3-5wt%, with the gross weight meter of B component.
7. isocyanate adhesive according to claim 1, it is characterised in that the NCO of the component A
Content is 29.5-32.1wt%, and the viscosity at 25 DEG C is 150-250mPas, preferred 180-230mPas.
8. one kind isocyanate adhesive by any one of claim 1-7 prepares polyurethane multilayer structures and answers
The method of condensation material, preparation process includes：
A. component A of the present invention is coated in the both sides of reinforcing material E；
B. in the side of polyurethane foam, repeat to implement following operation p time：Cover one layer and coat component A
Reinforcing material E, and the outer surface in reinforcing material E sprays B component；
C. in the opposite side of polyurethane foam described in step b, repeat to implement following operation q time：Cover one layer
The reinforcing material E of coating isocyanate component A, and the outer surface in reinforcing material E sprays B component,
Obtain multi-layer compound structure；
The upper and lower surface of the multi-layer compound structure for d. obtaining in step c is covered each by one layer of reinforcing material F,
Form multilayer composite；
E. the multilayer composite for step d being obtained is compressing in a mold, obtains polyurethane multilayer structures and answers
Condensation material；
Wherein p and q are identical or different, are separately the integer of 1-5, the integer of preferred 1-3.
9. isocyanate adhesive according to claim 8 prepares polyurethane multilayer structures composite
Method, it is characterised in that preparation process includes：
A. component A is coated in the both sides of Chopped Strand Mat；
B., the Chopped Strand Mat of the coating component A is covered in the both sides of thermoplasticity semi-hard polyurethane foam sheet,
And B component is sprayed in the outer surface both sides of Chopped Strand Mat, obtain three-layer composite structure；
C. non-woven fabrics is covered in the both sides of three-layer composite structure, forms five layers of complex；
D. it is five layers of complex is compressing in a mold, obtain polyurethane five-layer structure composite.
10. isocyanate adhesive according to claim 8 or claim 9 prepares polyurethane multilayer structures composite wood
The method of material, it is characterised in that the consumption of the component A is 60-120g/m2, preferred 70-100g/m2；B
The consumption of component is 10-50g/m2, preferred 20-30g/m2。
The polyurethane multilayer structures composite wood that 11. methods by any one of claim 8-10 are prepared
Application of the material in vehicles inner-decoration component, top, skylight preferably in the water, land and air vehicles,
Application in board putting things part, the application in top, skylight, board putting things part more preferably in automobile.
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| Title |
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| 李晓平等: ""醇对单组分湿固化异氰酸酯胶粘剂性能的影响"", 《中国胶粘剂》 * |
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