CN1009369B - Method of production of chemically hardening two-component materials based on polyurethanes and use - Google Patents

Method of production of chemically hardening two-component materials based on polyurethanes and use

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Publication number
CN1009369B
CN1009369B CN 85102027 CN85102027A CN1009369B CN 1009369 B CN1009369 B CN 1009369B CN 85102027 CN85102027 CN 85102027 CN 85102027 A CN85102027 A CN 85102027A CN 1009369 B CN1009369 B CN 1009369B
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China
Prior art keywords
component
prepolymer
acid
diisocyanate
isocyanato
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CN 85102027
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CN85102027A (en
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索尔
舍恩伯奇利
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Dow Automotive AG
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Gurit Essex AG
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Publication of CN1009369B publication Critical patent/CN1009369B/en
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Abstract

The present invention relates to a preparation method for chemical hardening two-component materials based on polyurethane. The method comprises the following three steps: step A. at least one kind of aliphatic series or aromatic diisocyanate or polyisocyanate reacts with polyol to prepare a prepolymer containing isocyanate end groups to serve as a first component; step B. the first component reacts with a base group at least containing two different hydrogen containing molecules to prepare the other prepolymer to serve as a second component; step C. the two components mutually react to prepare the material of the present invention. The material is particularly suitable for serving as self-hardening adhesive, paint, sealing materials, moulding materials, etc.

Description

Method of production of chemically hardening two-component materials based on polyurethanes and use
Involved in the present invention is is the two-component materials of the chemicosolidifying of major ingredient with urethane, has also set forth the method for manufacture and use thereof of these materials simultaneously.
We know, hardenable urethane illustrated in relevant document, for example, United States Patent (USP) 3,933, illustrated with single step process to make diphenylmethanediisocyanate carry out chemical reaction can the harden process of oligourethanes (Oligourethanes) of manufacturing for No. 725 with polyoxypropylene diols and polyoxypropylene triol.
United States Patent (USP) 3,707 has been set forth the process that excessive vulcabond is produced oligourethanes with the chemical reaction of polyoxy enediol for No. 521, obtains still to contain the goods of former isocyanate groups by these processes.Then, products obtained therefrom reacts with polyoxy alkene triol and generates branched urethane, contains the free isocyanate groups.
The goods that obtained according to the method (or similar method) that these patents disclosed are a kind of because of CO 2Effusion and cause the hardened product of inferior quality.The reaction scheme of the sclerosis of the active oligourethanes R-N=C=O of moisture below can proximate usefulness is illustrated:
Figure 85102027_IMG1
The sclerosis of making moist may cause the generation of harmful bubble, and hardenability depends on airborne water content on exhausted big degree, is difficult to control.Process of setting is inside from outermost layer lentamente
Layer expansion, while carries out in entire scope and do not resemble two-component materials.
Set forth the hardening technique of the oligourethanes that contains isocyanate groups in No. 30 19 356, Germany patent application, it has used the latent hardening agent, and for example, aldimine is with oxazolidine.Also recommended in the document to be used as the latent hardening agent with two enamines.Under these conditions, although added these stiffening agents, hardened speed still depends on moisture and the rate of diffusion of being transmitted by surrounding environment thereof.Equally, its sclerosis also be little by little from the outside to internal divergence, for thick-layer, just need the longer time.
The isocyanate functional groups protective material is recommended as follows in the urethane: hydroxymethyl ether, malonic ester, hexanolactam, phenol and ketoxime (about this point, see also Germany patent application 29 46 085; 25 42 500; 25 50 156 and 29 29 224).Yet, use protective material hardened shortcoming be need be higher temperature, often may cause the generation of bubble owing to cause the effusion of volatile products.
United States Patent (USP) 3,054 has been described for No. 755 by polyisocyanates with polyalkenyl glycol (polyalkenyl ether ethylene glycol) reaction, generates the process of urethane then with the reaction of amino alcohol.United States Patent (USP) 3,228, the prepolymer of having described to contain isocyanate group for No. 914 is with the reaction of amino alcohol.This material is depressed with adding at elevated temperature, finally is to come hardened by additional aromatic diisocyanate monomer.United States Patent (USP) 3,114 has been described the compound that is generated by amineothiot and amino two mercaptan and the terminal urethane resin reaction that has isocyanate group for No. 734.This material is to carry out sulfurized by the oxidation of thiohydroxy.
Above-described each pair component system all has weak point,, must use their component according to the stoichiometry mixing match fully usually that is, otherwise, the product that generates will have very big-difference, and its physical property often can not be satisfactory, and hardening strength is also let matters aside.The situation that does not need the stoichiometry mixing match usually is relevant with a kind of low molecule crosslinked vehicle.In this case, setting rate usually is so fast, and it is extremely difficult consequently controlling it,
Also will cause product to lack required physical property simultaneously.
It is found that, a kind of prepolymer (1) (has the free isocyanate functional group, from a kind of diisocyanate monomer or polyisocyanates, obtain) and by have a kind of prepolymer of isocyanate group by end, mix with reacting formed second component (2) one of in thiohydroxy alcohol, amino alcohol and same hydroxycarboxylic acid, thiocarboxylic acid or the aminocarboxylic acid simultaneously, the mixture that obtains has as beyond thought beneficial characteristics such as bonding, coating, packing and moulding materials.
The fixedly blending ratio of the advantageous feature of these materials and its component does not have confidential relation.They are easy to control and processing treatment, and noticeable especially advantage is: these hardened materials get soon and thoroughly, therefore also needn't be overheated in its depths, so do not have the bubble generation.
The purpose of this invention is to provide a kind of two-component materials, in this two-component materials, the oligourethanes and second component that contain free isocyanate groups group of common single-component are mixed together processing, compare with material is arranged earlier, can find following some improvements.
Two-component materials should be able to be in very wide variable ratio scope intermingling, and do not reduce quality.
Under hardened situation, product is uniform and stable all the time.
Than obtaining faster with the active oligourethanes of moisture and sclerosis more completely.
Can prevent generally speaking by CO 2With the formed bubble of the diffusion of other return volatile reactants.
Can simplify process of setting widely.
Another object of the present invention provides some simple coatings, sealing or bonding material, and these materials have the ideal physical property, particularly have improved elasticity, crushing load, breaking strength, tearing toughness and a uniform rigidity after snap cure.
Illustrate with sketch below:
Figure 85102027_IMG2
Therefore, problem of the present invention is a kind of two-component materials of the chemicosolidifying based on urethane, this material comprises: the prepolymer that has isocyanate end, as its first component, reaction product with the prepolymer that has isocyanate end and a kind of active compound effect gained, as its second component, this active compound has two hydrogenous molecular groupings at least, and with isocyanic ester different reactions takes place.The characteristics of this pair of constituent material are as follows:
The prepolymer of first component and second component is a reaction product, promptly by at least a aliphatics or aromatic diisocyanate monomer or polyisocyanates and be less than a normal at least a polyol reaction and form, polyvalent alcohol can be selected for use: polyethers, polythioether, polyester, polycaprolactone, polycaprolactam, polycarbonate, polyacrylic ester, polymethacrylate, urethane
And hydrocarbon polymer, at least two hydroxyls are all arranged in the molecule in each case.
For producing the mixture that used diisocyanate monomer of prepolymer or polyisocyanates can use following isocyanic ester or these isocyanic ester:
The toluylene group diisocyanate, diphenylmethanediisocyanate, 4,4 '-diphenyl diisocyanate, 4,4 '-two isocyanato-s-3,3 '-two chloro-biphenyl, 4,4 '-two isocyanato-s-3,3 '-dimethoxy-biphenyl, 4,4 '-two isocyanato-s-3,3 '-phenylbenzene-biphenyl, 4,4 '-two isocyanato-s-3,3 '-dimethyl-ditan, 1,5-naphthylidene-vulcabond, N, N '-(4,4 '-dimethyl-3,3 '-two isocyanato-s-biphenyl)-urethane, between-xylylene-vulcabond, 2,4,4 '-three isocyanato-s-biphenyl ether, 4,4 ', 4 " triphenyl methane-triisocyanate; three-(4-isocyanato-phenyl)-thiophosphatephosphorothioate; 1; 6-HDI; trimethyl-hexamethylene diisocyanate; 3-isocyanato-methyl-3,5,5-3-methyl cyclohexanol based isocyanate, (isophorone diisocyanate), instead-the 1.4-cyclohexyl diisocyanate, right-phenylene diisocyanate, tetramethyl--eylylene diisocyanate, 4,4 '-dicyclohexyl methane diisocyanate, 2,2-pair-(4-(6-isocyanato-acetyl oxygen)-phenyl) propane, polymethylene-polyphenylene isocyanic ester, the Desmodur(desmodur) L (Bayer Lever kusen be used to make the isocyanic ester of polyurethanes coating and foaming agent and the trade mark of isocyanate prepolymer class material), polyurethane binder N(Bayer, the trade mark of Leverkusen), the mixture of isocyanuric acid ester and these isocyanic ester.Polyvalent alcohol as prepolymer production can use polyethers, they can by following each epoxy compounds respectively polymerization produce, as, oxyethane, propylene oxide, butylene oxide ring, tetrahydrofuran (THF), Styryl oxide or epichlorohydrine, perhaps pass through these epoxide, propylene oxide particularly, be deposited on initial constituent up and down and be listed as the active hydrogen atom effect of each compound, as water, and alcohol, amine is as ethylene glycol, propylene glycol-1,2 and-1,3, butyleneglycol-1,2 and-1,4, hexylene glycol-1,6, TriMethylolPropane(TMP), the hexane triol, glycerol, trolamine, Sorbitol Powder, mannitol, sucrose, ammonia, thanomin or hexamethylene diamine polymerization produce.Their molecular-weight average is greater than 1,000, and usually from 2,500 to 7,000, the functionality of OH is generally 2.2 to 4 greater than 2.
Suitable polyester comprises the reaction product by polyvalent alcohol (normally binary or ternary) and polycarboxylic acid (normally binary) or carboxylic acid anhydride, or the reaction product of lower alcohol and carboxylicesters.Used carboxylic acid can comprise Succinic Acid, hexanodioic acid, suberic acid, nonane diacid, sebacic acid, phthalic acid, m-phthalic acid, benzenetricarboxylic acid, Tetra hydro Phthalic anhydride, tetrahydrochysene phthalate anhydride, tetrachloro-phthalic acid acid anhydride, Pyroglutaric acid, MALEIC ANHYDRIDE, fumaric acid, dimethyl terephthalate (DMT) and terephthalic acid-two-glycol ester.Polyvalent alcohol includes ethylene glycol, propylene glycol-1,2 and-1,3, butyleneglycol-1,4 and-2,3, hexylene glycol-1,6, ethohexadiol-1,8, glycerol, TriMethylolPropane(TMP), tetramethylolmethane, quinite, mannitol and Sorbitol Powder, methyl glycoside and glycol ether, polyoxyethylene glycol, dipropylene glycol and polypropylene glycol.
For example, belong to polycaprolactam row be by hexanolactam and binary or product that polyvalent alcohol obtained.
Polyacrylic ester and polymethacrylate are that the compound polymerization by following chemical formula forms:
CH 2=CH-CO-O-R-OH and CH 2= CO-O-R-OH
R in the following formula is a kind of more rudimentary alkenyl with 2 to 6 carbon atoms.Polyacrylic ester and polymethacrylate also can be formed by these compounds and other polymerisable ethene saturated compound copolymerization, 2 to 10 carbon atoms are arranged in these compound molecules, for example, vinylbenzene, vinylformic acid, fumeratine(fumaric acid), propylene, ethylene chloride and divinyl.
Polycarbonate with hydroxyl can comprise by following diatomic alcohol compounds as, propylene glycol-(1,3), butyleneglycol (1,4) and/or hexylene glycol-(1,6), glycol ether, triglycol, Tetraglycol 99 and diaryl carbonate as: diphenyl carbonate or carbonyl chloride react and prepare.
The molecular weight of urethane that can be used as the hydroxyl of polyvalent alcohol is 2,000 to 10,000, normally 4,000 to 8,000.Because their viscosity is very big, so they must react in a kind of being called in the softening oil usually, this generally speaking softening oil uses phthalic ester.For this reason, also can consider with its dibutylester, dioctyl ester, two isodecyl esters, two phenyl ester or butyl phenyl ester.
In some cases, can use catalyzer, for example, come accelerated reaction with the pink salt of carboxylic acid.Cause
This, people can use tin acetate, stannous octoate, tin laurate, oleic acid tin and dialkyl group-Xi-dicarboxylate, as: dibutyl tin acetate or dibutyl tin dilaurate etc. also have thiolic acid tin or tertiary amine.
An example as the bicomponent material production process, the prepolymer of the second component reaction product can be produced by the raw material of the prepolymer same composition that comprises with first component, and NCO content is 0.5 to 1.5 times (preferably 0.8 to 1.2 times) of the NCO amount of prepolymer in first component in the prepolymer of the second component reaction product.
Usually in order more to simplify, the first component prepolymer also can be used to produce second component, because fairly simple like this, product is more even, and can interreaction in bigger proportional range at bicomponent material under the situation that does not change its characteristic.In order to obtain certain effect,, can produce the prepolymer of a component by polyisocyanates, and produce the prepolymer of another component by vulcabond as in a component, obtaining bigger degree of crosslinking.Select for use different polyvalent alcohols to produce the possibility that prepolymer can access distinguishing resemblance.Second component is the reaction product of prepolymer and active compound, comprises bioactive molecule group in this active compound: hydrogen, hydroxyl, sulfydryl, amino and/or carboxyl.
So active compound can contain 2 to 6 (preferably 2 to 3, particularly 2) hydrogenous bioactive molecule groups.Such material has mercapto alcohol, amino alcohol, hydroxycarboxylic acid, thiocarboxylic acid or aminocarboxylic acid.Like this examples of substances comprise mercaptoethanol, mercapto-propanediol, dimercaprol dimercaptopropanol, monoethanolamine, aminopropanol, amino-propanediol, N-methylamino ethanol, N-methylamino propylene glycol, N-methylglucosamine, amino-phenol, hydroxyethyl piperazine, oxyacetic acid, lactic acid, thioglycolic acid, thiolactic acid, aminoacetic acid or Methionin.
In the reaction of the prepolymer of producing second component, should be specifically noted that guarantee formed reaction product be a kind of contain hydrogenous, can with the free molecule group of isocyanate reaction.According to the present invention, this result can be drawn by the following fact, promptly be used for the reactive activity compound have at least two different can with the reactive molecule group of isocyanic ester radical reaction.
According to the present invention, be based on the production process of the hardened bicomponent material of urethane: the prepolymer of first and second components be by at least a aliphatics or aromatic diisocyanate monomer or
Person's polyisocyanates forms less than at least a polyol reaction of its equivalent value, but this polyvalent alcohol polyethers, polythioether, polyester, polycaprolactone, polycaprolactam, polycarbonate, polyacrylic ester, polymethacrylate, urethane and hydrocarbon polymer.No matter select the sort of compound for use, have 2 hydroxyls in the molecule at least.
In implementing the necessary three kinds of reactions of the present invention, the ratio of its concrete quantity is as follows:
(1) vulcabond and polymeric polyisocyanate and polyvalent alcohol generate in the reaction of prepolymer, and its blending ratio still is left some free isocyanate end after being chosen such that i.e. reaction, and these end groups are used as final reaction or are used for preparing second component.The equivalent ratio of isocyanic ester and hydroxyl is about 1.3: 1 to 3 to 1.Proved already that specially suitable equivalent ratio was 1.5: 1 to 2.2: 1.
(2) generate in the reaction of second component for prepolymer,, will by definition, in the compound of reaction molecule, have 2 reactive functionality at least with 0.8 to 1.2 molar compound of reaction to each normal isocyanate functional group.This point has guaranteed that reaction product (i.e. second component) has and can carry out reactive activity group with the isocyanic ester group of first component that final product can be finished reaction thus.
(3) mixture ratio of final step (i.e. the mixing of two kinds of components) is not very strict.It can change in 0.8: 1 to 5: 1 scope.NCO in the normally used mixture: the equivalent ratio H(active hydrogen) be by 1: 1 to 5: 1(preferably 1.2: 1 to 2: 1) in general, used feed amount mixture, even blending ratio changes, also can with moisture phase reaction in the air that is presented under the final condition.
General reaction conditions:
Produce being reflected in 20 ° to 130 ℃ the temperature range of two components and carry out, be preferably in 40 ° to the 80 ℃ scopes, and under shielding gas (as, nitrogen), stir.If compound of reaction is not sufficient fluid, as mentioned above, the reaction in solvent is possible or even desirable.Yet, be not need solvent under many circumstances.As mentioned above, it also is possible using the catalyzer that quickens isocyanate reaction, and the reaction at the higher macromolecular compound that compares also is desirable simultaneously.Catalyzer additional and omitting can influence characteristic that compound keeps and hard
The change time.
The bicomponent material of producing according to the present invention can be used as gluing, coating, sealing-in and the compression moulding material of building structure, also can be used as the construction material of aircraft and steamer simultaneously.When they use as binding agent, but the sheet glass of sealing-in and bonding construction and installation sheet glass or vehicle and aircraft.They can be widely used for coating and the seal, sealing materials that the slab gluing is produced, be particularly suitable for the sealing-in of concrete structure, the coating of roofing, the covering on floor, as, the substrate of carpet, carpet, in general, when using as covering material, can be wear-resistant and skid, bump that can anti-stone in vehicle, aircraft and naval construction material.When using as plastic compression material or plastic compression fat, they can be used for producing plastic compression thing and cast thing, for example, but in electronic applications the various elements of compression moulding.
Usually these bicomponent materials can not use separately.They often use with other auxiliary agent and additive, as, fluidizer, solvent, filler and weighting agent, thickening material, protective agent and other can obtain the additive of better characteristic.For example, can improve the silane of clinging power characteristic.By priming paint and priming paint (for example, silane of having known and/or isocyanic ester), various materials all there is very good clinging power.
For refractory equipment, can mix into inhibition flame additive, as aluminium hydroxide, ANTIMONY TRIOXIDE SB 203 99.8 PCT or contain the additive (as polyvinyl chloride powder) of halogen.In order to improve conductivity, graphite or metal powder can be added in the material and be gone.In order to make it more inexpensive and improve wearing character, additional rubber meal or rubber grain also are possible.
Therefore, the present invention has also designed the use of mixture, and mixture is made up of the prepolymer that contains isocyanic ester and second component.Second component is to be generated with isocyanate reaction respectively by prepolymer that contains isocyanate end and active compound (this compound has 2 hydrogenous molecular groupings at least).Mixture can be used as self-hardening gluing, coating and seal, sealing materials.
To point out especially to be that the present invention has designed the application that mixture can be used as gluing, coating, sealing-in and the plastic compression material of self-hardening.Mixture is to be mixed by the prepolymer and second component.Contain isocyanate end in the prepolymer, and be to form by vulcabond or polymeric polyisocyanate monomer and polyol reaction.Second component composition be by prepolymer (may same or similar) and mercapto alcohol, amino alcohol, and hydroxyl, sulfo-or amino carboxylic acid reaction form.
Bicomponent material major advantage of the present invention is as follows:
(1) in view of with the first excessive component, by the airborne moisture excessive N CO group of can hardening, do not changing greatly under the situation of resulting product performance, the ratio of binary mixture (0.8: 1 to 5: 1) in the scope of broad changes.For the production of bicomponent material, usually not that the hand with the chemical analysis trainer carries out, under simple or even primary working conditions, this point is easy to obtain the product of uniform equal in quality.In contrast, with the production of the two-pack of known modern technique, the ratio that must very accurately manage mixture is so that obtain product with the characteristic that requires.Variation range (10~15%) according to known modern technique method may cause tangible downgrade.
(2) the one the second components by the blending ratio of having recommended (approximately from 1: 1 to 2: 1 or more than) can obtain product, under the interaction that does not have atmospheric moisture, form fully soon netted, and depth direction get with surface reaction (fully) the same fast.For the active oligourethanes that contains the isocyanate functional group of known moisture, this is a very big advantage, make this functional group (crosslinked) formation netted, and under the reaction of atmospheric moisture, harden to inside from the surface, on the other hand, CO 2Become unbound state, this free CO 2To cause containing the production of the porous material of pore.Netted formation and the sclerosis in the material thick-layer may need the several months long.
Example 1
A, first component (prepolymer)
With 4,4 of 1,250 gram '-diphenylmethanediisocyanate, in 70 ℃ nitrogen, making with molecular-weight average with stirring method is 2,000 4,500 gram polyether glycols reactions.Then, adding 2,900 restrains dioctyl phthalate (DOP)s and makes material further reaction under 70 ℃ of temperature.Then, add the polyether triol (molecular-weight average is 4,500) of 2,200 grams and the dibutyl tin dilaurate of 12 grams.(in this process temperature can not above 110 ℃) generation prepolymer after thermopositive reaction finishes, wherein isocyanate content is 1.6%.
B, second component
With 166 gram 2 mercapto ethanols, in 40 ℃ of temperature and resulting by routine 1-A
5,800 gram prepolymer reactions are till infrared spectrum no longer demonstrates any isocyanate group.Obtaining a kind of viscosity at 23 ℃ is the clearly faint yellow fluid of about 140 pascal seconds.
C, elastic coating material
First component of 100 grams is merged on a sheet glass with second component of 100 grams is mixed mutually, so that produce the thick-layer of an about 2mm.After 8 hours, material becomes netted, takes off on the slave plate then.The bullet colloid that obtains like this has good elasticity and tensile strength.
Example 2
We change 100 grams, second component in the processing of routine 1-C into 75 grams, produce a kind of similar bullet colloid 8 hours after, it is deposited just can obtain sufficient elasticity and tensile strength afterwards in 16 hours.
Example 3
When only using 50 grams, second component, can obtain and the analog result described in the example 2.
Example 4
A, in the planetary-type mixer under the vacuum condition, 7,000 grams, the first component prepolymer according to routine 1-A preparation is mixed with the pot of 1,000 gram kaolin black and 2,000 grams equably.Add the dibutyl tin laurate solution of 60 grams and mixing in a vacuum equably then.At this moment will obtain the noncurrent material of a kind of heavy-gravity, be poured in the filter cylinder then.
B, use the same method,, kaolin black with pot equably 7,000 grams, second component according to routine 1-B preparation and catalyst mix are poured out then.
C, according to 100 gram materials of routine 4-A preparation and 50 gram material mixing according to routine 4-B preparation.Will obtain a kind of seal, sealing materials of tension after several hours, its characteristic is shown in following table 1:
Table 1
Example 4 examples 5 examples 6
About 15 minutes about 15 minutes treatment time is about 15 minutes
After the non-adhesiveness 2 hours 1.5 hours afterwards 1 hour afterwards
Tensile strength:
0.5 newton/(millimeter) after 1 hour 20.8 newton/(millimeter) 21 newton/(millimeter) 2
3.5 newton/(millimeter) after 12 hours 23.5 newton/(millimeter) 23.5 newton/(millimeter) 2
As can be seen from Table 1: when changing the blending ratio of two kinds of components, it is very little that its characteristic goes up change relatively.
Example 5
As described in example 4, as by routine 4-A produced 100 gram components with 70 restrained components and mixed mutually by routine 4-B produces, will obtain a kind of sealing-in mixture with similar characteristics.
Example 6
As described in example 4, if the 100 gram components of producing by routine 4-A are mixed mutually with the 100 gram components of producing by routine 4-B, will obtain a kind of seal, sealing materials, but that this material forms netted lattice than the material of being produced by example 4 and example 5 is will be a little fast with similar characteristics.
Example 7 is to example 9
The production of A, second component
The method of this process and routine 1-B is similar, just with 161 monomethyl-ethanolamine that restrain
Replace 2 mercapto ethanol.
The production of B, seal, sealing materials
This process is all used the method similar with example 4 in all cases, with first components of 100 grams respectively with 50,75 and 100 second components that restrain, and do not make catalyzer in the use-case 4.
The characteristic of the product that is obtained is shown in following table 2:
Table 2
Example 7 examples 8 examples 9
First component, 100 grams, 100 grams, 100 grams
Second component, 50 grams, 70 grams, 100 grams
About 3 minutes about 3 minutes treatment time is about 3 minutes
20 minutes 20 minutes 20 minutes inviscid time
Tensile strength:
2.0 newton/(millimeter) after 1 hour 22.0 newton/(millimeter) 22.0 newton/(millimeter) 2
3.5 newton/(millimeter) after 4 hours 23.5 newton/(millimeter) 23.5 newton/(millimeter) 2
Example 10 is to example 12
The production of A, second component
The method of this production process and routine 1-B is similar, does not just use 2 mercapto ethanol and uses 275 gram N-(2-hydroxyethyls)-piperazine.
The production of B, coating material
In all cases, 100 grams, first component made of routine 1-A 100 grams, 70 grams and 50 restrain as stated above that A promptly uses the N-(2-hydroxyl respectively)-second component that piperazine makes mixes mutually.This compound is poured into the film that will obtain about 2 mm thick on the sheet glass.
This material forms netted lattice soon, only just can tear it down from sheet glass after two hours on pouring into sheet glass.After at room temperature shelving 4 hours, this film will have extraordinary elasticity and very high tensile strength.
Example 13 is to example 37
According to example 1, when 4,4 '-when diphenylmethanediisocyanate is replaced by following each compound of equivalent, can produce seal, sealing materials:
13, toluylene group diisocyanate.
14, diphenylmethanediisocyanate mixture of isomers.
15,4,4 '-diphenyl diisocyanate.
16,4,4 '-two isocyanato-s-3,3 '-DCBP.
17,4,4 '-two isocyanato-s-3,3 '-dimethoxy-biphenyl.
18,4,4 '-two isocyanato-s-3,3 '-phenylbenzene biphenyl.
19,4,4 '-two isocyanato-s-3,3 '-dimethyl diphenylmethane.
20,1,5-naphthylidene-vulcabond.
21, N, N '-(4,4 '-dimethyl-3,3 '-two isocyanato-biphenyl)-urethane.
22 ,-eylylene diisocyanate.
23,2,4,4 '-three isocyanato-biphenyl ethers.
24,4,4 ', 4 " triphenylmethane triisocyanates.
25, three-(4-isocyanato-phenyl)-thiophosphate.
26,1, the 6-HDI.
27, trimethyl-hexamethylene diisocyanate.
28,3-isocyanato-methyl-3,5,5-3-methyl cyclohexanol based isocyanate (different Buddhist
That ketone vulcabond).
29, anti--1, the 4-cyclohexyl diisocyanate.
30, right-phenylene diisocyanate.
31, tetramethyl--eylylene diisocyanate.
32,4,4 '-dicyclohexyl methane diisocyanate.
33,2, two (4-(6-isocyanato--acetyl the oxygen)-phenyl of 2-)-propane.
34, polymethylene polyphenylene isocyanic ester.
35, desmodur L (indicating the trade mark of Bayer and Leverkusen)
36, desmodur N (indicating Bayer and Leverkusen trade mark).
37, isocyanuric acid ester.
Example 38 is to example 50
According to example 1 and example 4, replace 2 mercapto ethanol mentioned among the routine 1-B can prepare gluing, coating and plastic compression material with the following compound of equal amount:
38, dimercaprol dimercaptopropanol.
39, mercapto-propanediol.
40, monoethanolamine.
41, amino-propanediol.
42, N-methylamino ethanol.
43, N-methylglucosamine.
44, amino phenol.
45, oxyacetic acid.
46, lactic acid.
47, thioglycolic acid.
48, thiolactic acid.
49, aminoacetic acid.
50, Methionin.
Example 51
The production of A, prepolymer
The dibutyl phthalate of the urethane (contain hydroxyl, molecular-weight average is 5,000, and the OH number is 28) of 2,000 grams with 2,700 grams mixed mutually with 10 gram dibutyl tin acetates.Then, add 4,4 of 350 grams '-diphenylmethanediisocyanate.With stirring method this material is reacted 70 ℃ of temperature.After finishing, reaction just obtained to have the prepolymer of 1.5% isocyanate content.
B, the second component production
Stirring down at 40 ℃ with 166 gram monomethyl-ethanolamine, till infrared spectra again be can't see isocyanate groups according to 6, the 200 gram prepolymers that routine 51-A obtained.
C, plastic compression material
Compound method according to routine 1-A, first component of 100 grams (by a kind of prepolymer of polyether glycol and polyether triol generation) is mixed mutually with 100 grams, second component of preparing by the method for example 51, will obtain the plastic compression material, also be suitable for the production of mould material simultaneously.

Claims (15)

1, but based on the production method of the hardened material of urethane, its feature comprises the following steps:
First kind of component is provided earlier, and this component has a kind of prepolymer with isocyanate end; Second kind of component is provided then, this component comprises a kind of prepolymer of being with isocyanate end and a kind of reaction product of active compound, this active compound has two kinds of different chemical molecular groups at least, contains the hydrogen that can be respectively reacts with isocyanic ester in this molecular grouping;
Above mentioned prepolymer be a kind of reaction product, promptly be at least a aliphatic or aromatic diisocyanate monomer or polyisocyanates and less than the reaction product of at least a polyvalent alcohol of its equivalent value;
Above-mentioned polyvalent alcohol can be polyethers, polythioether, polyester, pla-pcl, polycaprolactam, polycarbonate, polyacrylic ester, urethane and hydrocarbon polymer, in all cases, all has 2 hydroxyls in the molecule at least; The first above-mentioned component and second component are reacted.
2, according to the method for claim 1, be characterized in: the prepolymer of first component and second component will have similar identical functionality at least.
3, according to the method for claim 1 or 2, be characterized in: the prepolymer of first component and second component is to be produced by the isocyanic ester with identical Chemical Composition.
4, according to the method for claim 1 or 2, be characterized in: first component is to be produced by the polyprotonic acid with identical Chemical Composition with the second component prepolymer.
5, method according to claim 1 or 2, be characterized in: can be the toluylene group diisocyanate as monomer or the polyisocyanates of producing prepolymer, diphenylmethanediisocyanate, 4,4 '-diphenyl diisocyanate, 4,4 '-two isocyanato-s-3,3 '-two chloro-biphenyl, 4,4 '-two isocyanato-s-3,3 '-dimethoxy-biphenyl, 4,4 '-two isocyanato-s-3,3 '-phenylbenzene biphenyl, 4,4 '-two isocyanato-s-3,3 '-dimethyl diphenyl methane, 1, the 5-naphthalene diisocyanate, N, N '-(4,4 '-dimethyl-3,3 '-two isocyanato-biphenyl)-urethane, between-eylylene diisocyanate, 2,4,4 '-three isocyanato-biphenyl ethers, 4,4 ', 4 " triphenyl-methane triisocyanate; three-(4-isocyanato-phenyl)-thiophosphatephosphorothioate; 1; 6-HDI; trimethyl-hexamethylene diisocyanate; 3-isocyano compound 4-methyl-3,5,5-3-methyl cyclohexanol based isocyanate (isophorone diisocyanate), instead-1, the 4-cyclohexyl diisocyanate, right-phenylene diisocyanate, tetramethyl--eylylene diisocyanate 4,4 '-dicyclohexyl methane diisocyanate, 2,2-pair-(4-(6-isocyanato--hexanoyl-oxygen)-phenyl) propane, polymethylene-polyphenylene isocyanic ester, desmodur L and N, the mixture of isocyanuric acid ester or these isocyanic ester.
6, according to any one method in the claim 1,2 or 5, be characterized in: as the raw material of producing second component, the content of NCO is about 0.5 to 1.5 times of NCO content in the first component prepolymer in this prepolymer with prepolymer.
7, according to the method for claim 1, be characterized in: the reaction by prepolymer and active compound obtains second component, and this active compound contains hydroxyl, sulfydryl, amino and/or carboxyl as the bioactive molecule group that has reactive hydrogen.
8, according to the method for claim 7, be characterized in: carry out the reactive activity compound with prepolymer and contain 2 to 6 hydrogenous bioactive molecule groups.
9, according to the method for claim 7, be characterized in: prepolymer and mercaptoalcohol, amino alcohol or react with hydroxycarboxylic acid, thiocarboxylic acid or aminocarboxylic acid.
10, according to the method for claim 9, be characterized in: prepolymer and active compound react, this active compound can be mercaptoethanol, mercapto-propanediol, dimercaprol dimercaptopropanol, monoethanolamine, aminopropanol, amino-propanediol, N-methylamino ethanol, N-methylglucosamine, amino phenol, hydroxyethyl piperazine, oxyacetic acid, lactic acid, thioglycolic acid, thiolactic acid, aminoacetic acid or Methionin.
11, according at least a method in the claim 1,2 or 7, it is characterized in that: two kinds of components are by approximately from 0.8: 1 to 5: 1 NCO: the equivalent ratio interreaction H(activity).
12, according to the method for claim 6, be characterized in: the content of the NCO in the prepolymer of second component is about 0.8 to 1.2 times of NCO content in the pre-polymerization in first component.
13, according to the method for claim 8, be characterized in: active compound contains the hydrogenous bioactive molecule of the 2-3 that has an appointment group.
14, according to the method for claim 11, be characterized in: above-mentioned equivalent ratio is about 1.2: 1 to 2: 1.
15, according to the purposes of the mixture of a kind of or several method in claim 1 or the claim 2 to 14 preparation, be characterized in, can be used as the tackiness agent of self-hardening, coating, sealing material and moulding material or sulfurized tackiness agent, coating, sealing material and moulding material.
CN 85102027 1984-02-27 1985-04-01 Method of production of chemically hardening two-component materials based on polyurethanes and use Expired CN1009369B (en)

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CN 85102027 CN1009369B (en) 1984-02-27 1985-04-01 Method of production of chemically hardening two-component materials based on polyurethanes and use

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DE3407031A DE3407031A1 (en) 1984-02-27 1984-02-27 CHEMICAL-HARDENING TWO-COMPONENT DIMENSIONS BASED ON POLYURETHANES, METHOD FOR THE PRODUCTION OF A HARDENABLE DIMENSIONS BASED ON POLYURETHANE AND USE OF MIXTURES OF TWO COMPONENTS BASED ON POLYURETHANE
CN 85102027 CN1009369B (en) 1984-02-27 1985-04-01 Method of production of chemically hardening two-component materials based on polyurethanes and use

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