CN1054433A - Polyurea gel compositions and goods thereof - Google Patents
Polyurea gel compositions and goods thereof Download PDFInfo
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- CN1054433A CN1054433A CN 91101217 CN91101217A CN1054433A CN 1054433 A CN1054433 A CN 1054433A CN 91101217 CN91101217 CN 91101217 CN 91101217 A CN91101217 A CN 91101217A CN 1054433 A CN1054433 A CN 1054433A
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
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- 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
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- 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
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- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3225—Polyamines
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- C08G18/3256—Reaction products of polyamines with aldehydes or ketones
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- C08G18/40—High-molecular-weight compounds
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- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
- C08G18/5024—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups
- C08G18/503—Polyethers having heteroatoms other than oxygen having nitrogen containing primary and/or secondary amino groups being in latent form
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- 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
- C08G18/61—Polysiloxanes
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- 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
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
- C08G18/696—Polymers of conjugated dienes containing heteroatoms other than oxygen and other than the heteroatoms of copolymerised vinyl monomers
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
- C08G18/765—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group alpha, alpha, alpha', alpha', -tetraalkylxylylene diisocyanate or homologues substituted on the aromatic ring
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- 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
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
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- C08K5/00—Use of organic ingredients
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Abstract
Crosslinkable gelatinous composition fast setting obtains gelatinous composition, and they demonstrate chemistry and physical properties combines with the superior of resistance to deterioration.For substrate, especially electrical conductors, joint and the twist joint that need be protected from the environment, and for the sealing of jacketed cable, for example cable enters the sealing at link box place, and these compositions are particularly useful.
Description
The present invention relates to the curable composition that solidified gel and preparation gel are used.
The curing gel that comprises polyurethane gle just is used for sealing electricity component for a long time and protects metal construction to exempt from for example corrosion of seawater.For example, once used polyurethane gle round the cast-in-place of Stranded cable joint, its practice is component that will form gel (two or polymeric polyisocyanate and hydroxyl terminated poly-butadiene or polyester) and mixing diluents, then mixture is poured on apace around the joint and makes it solidify on the spot.Polymeric polyisocyanate/diol mixture at room temperature solidifies quite slow (for example, also taking several days even add catalyzer).In recent years, particularly resemble at United States Patent (USP) 4,600; 261 and 4,634, disclosed in 207(Debbaut); used the goods that are made of the Procuring gel to protect electricity contact and other substrate, the content of above-mentioned patent disclosure is here quoted as general reference.
Other known applications of gel comprises with organopolysiloxane gel and non-silicone gel, especially use Chang and Toy at European patent 0174165(1986) and Toy at European patent 0229102(1987) in the narration the butyl gel, with bus-bar and the insulation of other electricity component, these patents mentioned especially with this gellike in secondary terminal and joint as insulation composition and stress mediation composition.The disclosure of these two parts of applications is all here quoted as a reference.
The polyurethane gle that uses in the prior art has the physicals of good short-term, but ageing resistance is poor, promptly, aspect hydrolysis and these secular chemistry of thermostability, moisture resistance and incompressible deformability and physicals, especially be in higher following time of temperature in the use range of expection, performance is bad.In addition, polyurethane gle can extract softening agent in some cases or otherwise damage its function from the polyvinyl chloride insulation body.
We have found new gelatinous composition, and it can be used for sealing and isolated environment is come at the bottom of the protecting group, especially the electricity web member.This new composition unexpectedly demonstrates tensile strength, stretchiness, obdurability, with substrate (comprising the substrate that contains polyvinyl chloride) consistency, can absorb the Macrodilution agent and not have the superior of character such as obvious syneresis and effectively combine, simultaneously keep favourable viscosity again, this is very important for the gel sealant composition.
One aspect of the present invention provides a kind of composition that contains crosslinked polyureas.This crosslinked polyureas preferably exists with the form of gel.This composition preferably also has polyurea gel, and its Voland hardness is 1 to 500 gram, and elongation limit is at least 50%.Preferably, polyurea gel contains from 25%(weight at least) to 95%(weight) thinner (based on the weight of polyureas and thinner and).Contain from 25%(weight at least) to 95%(weight) polyurea gel of thinner, its gel fraction accounts for the 5%(weight of polyureas and thinner gross weight) to 75%(weight) then better.Preferably, thinner contains a kind of liquid that can compatible with crosslinked polyureas (for example swelling), and is not chemically prepared the used condition influence of crosslinked polyureas.
In another aspect of this invention, the molecular-weight average in the polyureas between the urea groups is less than every moles of polymer 500 grams, for example less than every moles of polymer 250 grams.Have the polyureas of such urea groups density, particularly useful in the occasion that needs high-k.In some purposes, for example in the occasion that needs the low-k gel, molecular-weight average may be wished greater than 500 between urea groups, for example is at least every moles of polymer 1000 grams.Even wish that every moles of polymer at least 2000 restrains.
" crosslinked " speech is meant the covalent linkage that forms by chemical reaction between two crosslinkable positions in this specification sheets, stretches out from these positions and adds up to three or more molecule segments; Or referring to minimum two covalent linkage, each forms by the chemical reaction between crosslinkable position and the middle element, so the remainder of middle element has at least three molecule segments to be gone out by its stretching, extension.Intermediate compound normally contains the low-molecular weight compound or the low-molecular-weight oligomer of at least three crosslinkable positions.Crosslinked can be (T shape connects, and, the crosslinked of three unfolded chain sections is arranged that is) or four functional (H shape connects, and, the crosslinked of four unfolded chain sections is arranged that is) of trifunctional, also higher functionality can be arranged.
On the other hand, the invention provides a kind of compositions crosslinkable, its Voland hardness when completely solidified is 1 to 500 gram, elongation limit is at least 50%, this curable composition comprises the first kind of organic compound that contains amido, second kind of organic compound and a kind of thinner that comprises isocyanate group or isocyanic ester precursor group, and the quantity of thinner accounts for the 25%(weight of first kind of organic compound, second kind of organic compound and thinner weight sum) to 95%(weight).In a preferred embodiment, first kind of organic compound is the polyamine that each molecule contains an average out to n amido, second kind of organic compound is polymeric polyisocyanate or polymeric polyisocyanate precursor, contain m isocyanate group or isocyanic ester precursor group in the per molecule, above-mentioned n and m all are at least 2, n and m sum are at least 4.1, and composition is less than 600 seconds 25 ℃ gelation time (being defined as follows) when not adding catalyzer.
On the other hand, the invention provides cover complexes, it comprises at least two containers, and each container contains at least a material that is selected from in next group material:
(1) first of amino-contained kind of organic compound;
(2) contain second kind of organic compound of isocyanate group or isocyanic ester precursor group; With
(3) a kind of thinner that does not react with first and second kind organic compound, the total amount of thinner is the 25%(weight of first organic compound in the container, second organic compound and thinner weight sum in the container) to 95%(weight).
The distribution of these materials in container should make container when room temperature (25 ℃) is preserved 6 months under drying conditions, and first kind and second kind of organic compound are stable;
When the content of container mixes also fully curing, obtain crosslinked polyurea gel, its Voland hardness is 1 to 500 gram, elongation limit is at least 50%.
In this one side of the present invention, preferably, first kind of organic compound is the polyamine that per molecule contains an average out to n amido, second kind of compound is polymeric polyisocyanate or the polymeric polyisocyanate precursor that per molecule contains an average out to m isocyanate group or isocyanic ester precursor group, above-mentioned n and m all are at least 2, and n and m sum are at least 4.1.
Another aspect of the present invention provides a kind of method that forms polyurea gel, and the Voland hardness of this gel is 1 to 500 gram, and elongation limit is at least 50%, and aforesaid method comprises and exists next to react at thinner following two kinds of materials
(1) first of amino-contained kind of organic compound; With
(2) contain second kind of organic compound of isocyanate group or isocyanic ester precursor group; Thinner does not react with first and second kinds of organic compound, and its consumption is the weight of 25%(at least of first kind of organic compound, second kind of organic compound and thinner weight sum) to 95%(weight).In this one side of the present invention, preferably, first kind of organic compound is the polyamine that per molecule contains an average out to n amido, second kind of organic compound is polymeric polyisocyanate or the polymeric polyisocyanate precursor that per molecule contains an average out to m isocyanate group or isocyanic ester precursor group, above-mentioned n and m all are at least 2, and n and m sum are at least 4.1.
On the other hand, the invention provides a kind of goods that are used at the bottom of the protecting group, it comprises a kind of composition that contains polyurea gel, and the Voland hardness of composition is from 1 to 500 gram, and elongation limit is at least 50%.These goods also include be used to make the solidified gel deformation in case with the contacted device of substrate, preferably make after the solidified gel deformation with substrate closely and proper device that contacts.
On the other hand, the invention provides a kind of substrate, it is contained the composition that solidifies polyurea gel at least in part and is sealed, and the Voland hardness of said composition is 1 to 500 gram, and elongation limit is at least 50%.
On the other hand, the invention provides a kind of method that substrate is sealed, comprise with containing following mixture of ingredients and surround substrate, and the mixture solidified that contacts with substrate of order:
(1) first of amino-contained kind of organic compound;
(2) contain second kind of organic compound of isocyanate group or isocyanic ester precursor group;
(3) a kind of thinner, it is in the influence that chemically is not subjected to react between first kind of organic compound and the second kind of organic compound, and its quantity is the weight of 25%(at least of first kind of organic compound, second kind of organic compound and thinner gross weight) to 95%(weight).
In this one side of the present invention, preferably, first kind of organic compound is that polyureas, second kind of organic compound that per molecule contains an average n amido is polymeric polyisocyanate or the polymeric polyisocyanate precursor that per molecule contains an average m isocyanate group or isocyanic ester precursor group, above-mentioned n and m all are at least 2, and n and m sum are at least 4.1.
Another aspect of the present invention provides the method at the bottom of a kind of protecting group, comprising:
(1) provides a kind of solidified polyurea gel;
(2) the solidified polyurea gel is applied in the substrate, makes composition basically at least a portion substrate be sealed.
Another aspect of the present invention provides the method at the bottom of a kind of protecting group, comprising:
(1) provide a kind of composition that contains crosslinked polyureas, the Voland hardness of composition is 1 to 500 gram, and elongation limit is at least 50%;
(2) composition is applied in the substrate, makes composition basically at least a portion substrate be surrounded.
Another aspect of the present invention provides composition that a kind of preparation has predetermined specific inductivity and composition has been solidified into the method for crosslinked polyurea gel, and the preparation method for compositions comprises:
(A) adulterant of selection thinner, wherein the specific inductivity of each thinner is different, and it is desired numerical value that the weight ratio of selection thinner makes the specific inductivity of adulterant; With
(B) above-mentioned adulterant is added in a kind of composition, composition includes first kind of organic compound of amino-contained and contains second kind of organic compound of isocyanate group or isocyanic ester precursor group; The relative proportion of adulterant and quantity make composition exhibiting go out predetermined dielectric constant.
Of the present invention aspect these in, thinner preferably is made of multi-component mixture under a lot of situations, wherein at least one component at room temperature is a liquid, and its specific inductivity and another component at least is different.
Fig. 1 shows how the hardness of curing polyurea gel of the present invention becomes with urea concentration or cross-linking density (triamine content in triamine/diamines adulterant).
Fig. 2 represents how gelation time becomes with polymer concentration.
Fig. 3 represents that the viscosity of curing polyurea gel of one embodiment of the present invention is how with the variation of polymer concentration and cross-linking density (triamine content in triamine/diamines adulterant).
In the present invention, the molecular-weight average (Mc) that solidifies between the polyurea gel cross-link bond should be at least 2000, and for example at least 4000, preferably at least 7500, for example at least 10000, in some concrete enforcement at least 20000.The Voland hardness of composition is preferably 2 to 375 grams.Particularly 2 to 125 restrain.Preferably 2 to 40 restrain.The elongation limit of composition preferably is at least 250%, particularly is at least 650%, and for example at least 700%, preferably at least 800%.
First kind of used (containing amine) compound can be the independent a kind of compound or the mixture of several compounds when preparing these new gels, for example, can be to have the compound that has two amidos in the compound of 3 amidos and/or one or more each molecules at least in one or more each molecules at least.Second kind of (containing isocyanic ester or isocyanic ester precursor) compound similarly can be the independent a kind of compound or the mixture of several compounds, for example, can be that one or more each molecules have the compound of at least three reactive groups and/or the compound that one or more each molecules have two reactive groups at least.The molar equivalent of first kind of compound or combination of compounds and second kind of compound or combination of compounds is than preferably, most of molecule of reactant is connected (promptly by other molecule of at least two cross-link bonds and one or several, formed closed level, it has constituted at least a portion three degree reticulated structures).Be preferably at least 50%, for example at least 65%, preferably at least 75% cross-link bond forms this closed level.For this reason, the molar equivalent of first kind of compound or combination of compounds and second kind of compound or combination of compounds is relatively good to be from 0.67: 1 to 1.5: 1, for example, 0.8: 1 to 1.25: 1, preferably 0.9: 1 to 1.11: 1.
Polyurea gel can be a solidified (that is, with solidify earlier before substrate contacts) in advance, also can with curing again after substrate contact.If gel solidifies in advance, fits best has utilizes compression method to make solidified polyurea gel distortion so that the device that contacts with substrate with contacted device of substrate and/or maintenance solidified polyurea gel.
The cohesive strength of curing polyurea gel of the present invention and gelatinous composition is more preferably greater than the bond strength of gel or gelatinous composition.
Composition of the present invention contains at least 25%, for example at least 30% preferably, and preferably at least 45%, at least 60% thinner for example, above-mentioned percentage ratio represents to account for the weight percentage of crosslinked polyureas and thinner gross weight.Preferably the thinner that usage quantity is suitable with above-mentioned scope prepares gel and/or gelatinous composition.
Preferably first kind of organic compound has following chemical formula:
Second kind of organic compound has following chemical formula:
Wherein h, j, i and k can be identical or different, and they are and are at least 1 integer, and h, j, i and k sum are at least 20, but less than 200;
Each Q group is primary amine groups or the secondary amine that directly links to each other with the carbon atom of A group, can be identical or different;
Each P group is isocyanate group or the isocyanic ester precursor group that directly links to each other with the carbon atom of A group, can be identical or different;
Each A group can be identical or different, and its chemical formula is-R--R-O-R-,-R-CO
2-R-,-R-NH-CO-R-,-R-NH-CO
2-R-,-R-S-R-,-O-Si(R ')
2-or-O-Si(R ')
2-R-, wherein each R group is alkylidene group, substituted alkylene, alkenylene, replacement alkenylene, arylidene or replaces arylidene, can be identical or inequality, each R ' group is alkyl, substituted alkyl, aryl or substituted aryl, can be identical or different;
Each D group can be identical or inequality, and they are a valence link or secondary amine, or alkylidene group, substituted alkylene, alkenylene, replacement alkenylene, aryl or replacement arylidene;
Each E group can be identical or inequality, and they are a valence link or alkylidene group, substituted alkylene, alkenylene, replacement alkenylene, arylidene or replace arylidene.
Valence link one speech is meant an independent covalent linkage, and it directly links together two atoms of first kind of compound or second kind of compound main chain.
The isocyanic ester precursor group is a kind of group that can form isocyanate group under the reaction conditions of preparation polyurea gel; for example; a kind of protected isocyanate groups; promptly; a kind of isocyanate groups process contains the processing (reaction) of the compound (for example malonic ester of replacement or unsubstituted phenol, oxime or alkyl replacement) of reactive hydrogen atom, obtains a kind of inactive relatively compound, utilizes heating; for example be heated to 150 ℃, can produce isocyanic ester again by it.This inactive relatively examples for compounds comprises that the phenol or the fragrant oxime that replace by isocyanic ester and alkyl react the carbamate that makes.Protecting group can only be sloughed with the method for heating, or with protected isocyanic ester and monomer that also contains reactive hydrogen atom or polymerizable compound (for example aliphatic series or aromatic amine and alcohol) reaction, sloughs protecting group.
Suitable amine includes but not limited to the end capped polyoxypropylene of alpha-amino group propyl group, omega-amino-of molecular weight from 200 to 20000, the end capped polyoxyethylene of alpha-amino group ethyl, omega-amino-of molecular weight from 200 to 20000, the end capped polyoxy butylene of alpha-amino group ethyl, omega-amino-of molecular weight from 250 to 25000 etc.; Approximate construction is as the dimerization diamines of (I):
With the polyamide resin that is rich in amine, for example dimerization diacid (approximate construction is as (II)) or other dicarboxylic acid and excessive replacement or the reaction product of unsubstituting alkylidene or arylidene diamines;
And the end capped amine-epoxy adduct of amido, for example reaction product of bisphenol A epoxide resin and diamines (as diethylenetriamine); 4,4 '-diamino-3,3 '-the dimethyl dicyclohexyl methyl hydride; Aromatic amine, for example diaminodiphenylsulfone(DDS), ethylene dianiline, methylene dianiline (MDA), diethyl toluene diamine, 3,5-diformazan sulfenyl-2,4-tolylene diamine etc.; The end capped polyhutadiene of amine, the end capped perbutan of amine and the end capped polysiloxane of amine.As the end capped polydimethylsiloxane of aminopropyl dimethyl, the end capped polydimethylsiloxane of ammonia butyl dimethyl etc.The trade name that can buy from Henkel company that has that can mention among the suitable polymeric amide that is rich in amine is the polymeric amide of Versamid 100, Versamid 115, Versamid 125 and Versamid 140.That can mention among suitable epoxy-amine affixture has those that Henkel company sells with trade name Versamine, for example a Versamine C30.
Suitable polymeric polyisocyanate or its precursor comprise the organic isocyanate that at least two isocyanate group are arranged in each molecule.Polymeric polyisocyanate can have low, high or medium molecular weight, and can be any in the organic polymeric polyisocyanate of many kinds, comprise ethylidene diisocyanate, trimethylene diisocyanate, ten dimethylene diisocyanates, hexamethylene diisocyanate, hexamethylene diisocyanate trimer, four ethylidene diisocyanates, pentamethylene diisocyanate, propylidene-1, the 2-vulcabond, 2,3-dimethyl tetramethylene diisocyanate, 1,4-two isocyanato-hexanaphthenes, methyl-hexamethylene diisocyanate, 3-isocyanato-methyl-3,5,5-3-methyl cyclohexanol based isocyanate, cyclopentenes-1, the 3-vulcabond, to phenylene vulcabond, naphthalene diisocyanate, 4,4 '-the diphenylene methane vulcabond, 4,4 '-diphenylene propane vulcabond, tetramethyl-eylylene diisocyanate (TMXDI), 1,2,3,4-four isocyanato-butane, butane-1,2, the 3-triisocyanate, and the fragrant paracyanogen acid esters that contains the linearity and the branching of isocyanic ester, it can be a polymeric in itself, for example polyethers and polyester prepolyer polymeric polyisocyanate.The representative example of this class prepolymer is commodity Desmocap 11A and the Desmocap 12 that Mobay company sells.
Thinner can be any organic liquid that has with the consistency of degree that polyureas requires.Therefore cross linked gel of the present invention can be prepared into the solubility parameter with very wide scope.Particularly, the solubility parameter of gelatinous composition provided by the invention, can than consider to use so far, those height above-mentioned for example.Correspondingly, in some purposes, the solubility parameter of thinner is at least 8.0 better to be at least 7.6 Hildebrands (Hildebrand) for good, preferably is at least 9.0.Suitable diluent comprises mineral oil, aliphatic hydrocarbon ils, and for example with those hydrocarbon ils of " Permethyl " trade name sale, its universal architecture formula is H (C(CH
3)
2)
n-H, wherein n is greater than 10, and viscosity is that about 35 centipoises are to about 50 centipoises; To small part fragrance, polycyclic hydrocarbon ils preferably, for example partially hydrogenated terphenyl; The ester of aliphatic series, fragrance and mineral acid, these esters comprise di (2-ethylhexyl) phthalate, phthalic acid two (tridecyl) ester, tri trimellitate ethylhexyl, dibutyl phthalate, butyl benzyl phthalate, diethyl phthalate, phosphoric acid ethylhexyl diphenyl, Tritolyl Phosphate, phosphoric acid trimethylphenylmethane base diphenyl; And sulphonamide, for example N-ethyl-neighbour, right-toluol sulfonamide; Siloxane fluid, for example viscosity is from about 1 centipoise to 10
6Mentioned in the dimethyl siloxane of centipoise (as the International Patent Application WO 90/10035(1990 of Dubrow in announcement), the disclosed content of this application is here quoted as a reference); And the mixture of similar substance and above-mentioned any two or more materials.The difference of the solubility parameter of gel and the solubility parameter of thinner (if liquid diluent is a kind of incessantly, then being the average solubility parameter of thinner) should be less than 2 Hildebrands, less than 1 better, be preferably less than 0.5.
If desired, can comprise in the reactant that one or more oxy-compound are as thinner.We find that amine is more faster than oxy-compound with the reaction of isocyanic ester or isocyanic ester precursor compound, so that the latter plays inert diluent basically.
Curable composition of the present invention and composition manufactured according to the present invention can contain various annexing ingredients, for example fire retardant, corrosion inhibitor, antioxidant, UV light stabilizing agent, sterilant and other biocides, pigment and increase or reduce thermal conductivity and the filler of specific conductivity and regulate density or the filler of other physical properties.These additives or filler also can be used for regulating or influence and solidify and crosslinked speed or degree, and the whole casting that influences final composition.Dittmer and Dubrow are at United States Patent (USP) 4,852,646(1989) and the European patent application EP 0 announced of Holland and Rost, 324, those components of mentioning 255(1989) are particularly useful for being spiked in the gel of the present invention, and these two parts of disclosed contents of file are here quoted as a reference.
Polyurea gel of the present invention preferably contains stablizer and antioxidant, for example, in the following material one or more: 1,6-hexa-methylene two (3,5-di-t-butyl-4-hydroxyl hydrogenated cinnamate), four (methylene radical 3-(3 ', 5 '-di-t-butyl-4 '-hydroxyphenyl) propionic ester) methane, octadecyl 3-(3 ', 5 '-di-t-butyl-4 '-hydroxyphenyl) propionic ester, N, N '-two (3-(3 ', 5 '-di-t-butyl-4 '-hydroxyphenyl) propionic ester) hydrazine, sulfo-di ethylene bis (3,5-di-t-butyl-4-hydroxyl hydrogenated cinnamate), triglycol two (3-(3 '-tertiary butyl-4 '-hydroxyl-5 '-aminomethyl phenyl) propionic ester), octadecyl-3(3 ', 5 '-di-t-butyl-4 '-hydroxyphenyl) propionic ester, N, N '-hexa-methylene two (3,5-di-t-butyl-4-hydroxyl hydrocinnamamide), 2-methyl-4, two ((hot sulfenyl) methyl) phenol of 6-, 4,4 '-thiobis (6-tertiary butyl meta-cresol) 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol), 4,4 '-methylene-bis (2, the 6-di-tert-butylphenol), di-tert-butylphenol, 2,2 '-methylene-bis (the 4-ethyl-6-tertiary butyl) phenol, the reaction product of Dicyclopentadiene (DCPD) and o-tert-butyl hydroxytoluene, 2(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2(2 '-hydroxyl-3 ', 5 '-di-tert-pentyl-phenyl) benzotriazole, 2(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-the 5-chlorobenzotriazole, two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate, Succinic acid dimethylester and 4-hydroxyl-2,2,6,6-tetramethyl--1-piperidines alcoholic acid condensation product, two (2,2,6,6-tetramethyl--4-piperidyl) sebate, { (3, two (1, the 1-the dimethyl ethyl)-4-hydroxyphenyl of 5-) methyl } butyl-two (1,2,2,6,6-pentamethyl--4-piperidyl) ester, two (O-ethyls (3, the 5-di-tert-butyl-4-hydroxyl benzyl) phospho acid nickel, 4,4 '-two (α, α-Er Jiajibianji) pentanoic, the condensation reaction products of pentanoic and acetone, the pentanoic of virtueization, the pentanoic of octyl groupization, poly-((6-((1,1,3, the 3-tetramethyl butyl) amino)-s-triazine-2,4-two bases) ((2,2,6,6-tetramethyl--4-piperidyl) imino-) hexa-methylene ((2,2,6,6-tetramethyl--4-piperidyl) imino-)), zinc dialkyl dithiocarbamate, zinc dialkyl dithiophosphate, the thio-2 acid dialkyl, the distearyl pentaerythritol diphosphites, three nonyl phenyl phosphites, hydrogenation phospho acid two lauryls, tricresyl phosphite (3, the 5-di-tert-butyl-phenyl) ester, four (3, the 5-di-tert-butyl-phenyl)-4,4 '-the biphenylene diphosphites, polycarbodiimide etc.
In order to have higher oxidative stability, polyurea gel of the present invention preferably " is rich in amine ", promptly, the ratio of amine and isocyanic ester is greater than 1 in being used for preparing the starting raw material of polyureas, for example greater than 1.02 to 1, preferably greater than 1.05 to 1, for example greater than 1.1 to 1.
Used " gelation time " speech is meant from isocyanic ester, amine and other composition mixture time institute's elapsed time that no longer flows under own wt that mixes at first in this specification sheets.This can also be observed the container lean of splendid attire reactive component whether to flow quite simply constantly and judge.Repeatability can reach+and 25%.Gelation time under 25 ℃ should be less than 900 seconds, less than 600 seconds better, less than 600 seconds, for example then better, be preferably less than 100 seconds, especially less than 50 seconds less than 200 seconds.
The following example explanation the present invention.
Embodiment 1
Prepare polyureas with isocyanic ester
Narrated to this step summary and made the prescription 1-1 that lists below to the used method of 1-15.Every kind of gel prepares with three kinds of basal components, promptly
1) structure is suc as formula the tetramethyl-eylylene diisocyanate (TMXDI of (1), can buy from American Cyanamid company) and approximate construction suc as formula the vulcabond dimer (DDI1410 of (2), can buy from Henkel company) mixture, its quantity is listed in table 2.
2) the end capped polypropylene ether of a kind of amine (Jeffamine D-4000, its molecular weight are 4000, and each molecule contains about two amidos, or similar Jeffamine T-5000, and its molecular weight is 5000, and each molecule contains about three amidos).
3) inert diluent that table 1 is listed below.
We find, even the reaction of isocyanic ester and amine is also carried out very soon when diluting greatly with extender, so are sought after as isocyanic ester (part A) with as two kinds of masterbatch (masterbatch) of amine (part B).Two kinds of masterbatch contain usually equal-volume or etc. the material of weight, mix soon and begin reaction.Part A contains isocyanic ester, part thinner, stablizer and filler etc.Part B contains amine, remaining thinner and stablizer etc.
When the preparation gel, each component of proper amt is weighed on analytical balance (being accurate to 0.01 gram) is blended into part A and part B in following all embodiment.Then part A and part B are mixed (observed and be as short as 10 seconds gelation time) rapidly and be cast in the beaker or flat board on.Usually gel is cast to fast the interior and curing at room temperature of mould of one 6 inches * 6 inches * 0.125 inch (15.24 * 15.24 * 0.3175 centimetre).After solidifying 24 hours under the room temperature, measure the character of gel at gel.Elongation is used from the next tensile bars of molded sheet die cut by the step described in the ASTM D419 and is measured.For measuring hardness, place 100 ml beakers to solidify 60 gram blended prescription materials.Measure hardness with LFRA-1000 type Voland-Stevens structural analysis instrument, this instrument has the trigger of one 5 gram on 1/4 inch (0.635 centimetre) spheric probe.Probe enters 4 millimeters of gels downwards with the speed of 0.2 millimeter of per second.After initial hardness is measured 1 minute, probe is remained on the hardness of resurveying on the constant mid-depth, with percentage ratio the measuring of hardness minimizing as stress relaxation.The extraction of will popping one's head in after having surveyed hardness is with observed maximum, force measuring as viscosity.For the gel that makes as thinner with DBP, gained the results are shown in table 2.
Embodiment 2
Table 3 has been listed several physical propertiess that choose of gel with the step preparation of embodiment 1, used polyetheramine (Jeffamine D-2000 during the preparation gel, it is the end capped polyoxypropylene of amine of molecular weight 2000, each molecule on average has two terminal amidos, can buy from Texaco chemical company) and the various mixtures of T-5000, and be added with the dibutyl phthalate (DBP) of different concns or the mixture of Phosflex 362(di(2-ethylhexyl)phosphate phenyl octyl group ester/triphenylphosphate) as thinner.
Embodiment 3
Prepare polyureas with protected isocyanic ester
Narrated to this step summary the used method of prescription of making the example 4-1 to 4-19 that lists below, these prescriptions have constituted gel of the present invention.Every kind of gel is prepared by four kinds of basal components:
1) protected isocyanic ester: the two all can buy Desmocap 11A and Desmocap 12(from Mobay company).Desmocap 11A(equivalent is about 1750) be three-functionality-degree, Desmocap 12(equivalent is about 2470) be the protected oligomeric isocyanates of two functionality, make by polypropylene glycol, tolylene diisocyanate and alkylphenol.
2) solidifying agent: the end capped polyoxypropylene of amine (Jeffamine D-400 or Jeffamine D-2000 can buy from Texaco company) or 4,4 '-diamino-3,3 '-dimethyl dicyclohexyl methyl hydride (DDD can buy from BASF AG).Jeffamine D-400(molecular weight about 400) and D-2000(molecular weight about 2000) be two functional amine end-blocking polypropylene ether oligopolymer.
3) antioxidant: Irganox 1035, CibaGeigy company produces.
4) thinner: phthalic ester, with dioctyl phthalate (DOP) (DOP can obtain from Aldrich chemical company) or phthalic acid two (tridecyl) ester (DTDP can obtain from Exxon chemical company).
The consumption of component 3 is 1% of mixture in all prescriptions.Each component of weighing on analytical balance (accurately to 0.01 gram) is mixed with the overhead stirrer that has the spiral lodicule then.Mixed mixture is poured in the mould of 6 inches * 6 inches * 0.125 inch (15.24 * 15.24 * 0.3175 centimetre), in air circulating oven, solidified 17 hours in 120 ℃.Use the tensile bars that cross cutting gets off from molded sheet to measure elongation according to the described step of ASTM D419.The 12 gram mixtures of in three 20 milliliters scintillation vial, packing into, in air circulating oven in 120 ℃ of dryings 17 hours to carry out hardness measurement.The sample of various prescriptions is all measured hardness as above-mentioned with Voland structural analysis instrument.The results are shown in table 4.
Embodiment 4
Adopt the step of embodiment 3 to prepare gel, initial substance is a kind of two functional amines 4,4 '-diamino-3,3 '-dimethyl dicyclohexyl methyl hydride (DDD, equivalent 119) and isocyanate-terminated urethane (the Desmocap 11A of branching, can buy from Mobay company) with have the various mixtures of the linear fragrant urethane (Desmocap 12, can buy from Mobay company) of ether.First kind of above-mentioned urethane contains the 2.4% protected isocyanate group of having an appointment, and equivalent is about 1750; A kind of urethane in back contains the 1.7% protected isocyanate group of having an appointment, and equivalent is about 2470.These gels are to prepare under the condition of the dioctyl phthalate (DOP) existence of different concns.The results are shown in the table 5.
Embodiment 5
Adopt the general step of embodiment 1, by various diamines and (or) triamine prepares gel.Used prescription and qualification result are shown in table 6,7 and 8.In table 6, gel sample 6-1 to 6-12 has illustrated the character of gained gel when using Therminol 66 as thinner and change polyureas concentration.Gel sample 6-13 has omitted Jeffamine D2000, but all similar in others.In table 7, the gel that gel sample 7-1 and 7-2 representative makes as thinner with the mixture of Shellflex 371 and Santicizer 141 or DEP.Gel sample 7-3 to 7-7 has represented that how gelling properties changes with the concentration of polyureas.In table 8, used many kinds of thinners to prepare gel.Gel sample 8-5 to 8-8 is illustrated in under the condition of HB-40 as thinner and the different diamines/triamine ratio of employing, and polymer concentration is how the character of 20% gel changes.Gel sample 8-9 use polyvalent alcohol (PPG-1025) and a kind of amine prepare the polyurea gel in the polyvalent alcohol thinner.In sample 8-14, the composition that is used for preparing gel is added with stablizer (Irganox 1090 of Ciba-Geigy company).Gel sample 8-20 to 8-23 represents how diluent mixture can change to change the solubility parameter of gel.
Table 7 is annotated: b) Shellflex 371; D) Santicizer 141; E) DEP;
The concentration of polyureas in gelatinous composition
Table 8 is annotated:
C) Santicizer 154; D) Santicizer 141; E) DEP; F) HB-40; G) DBP; H) Santicizer 160; I) D4000; J) PPG-1025; K) Phosphlex 362; L) Jayflex DTDP; M) Ketjenflex 8 antioxidant n); P) TOTM;
6 millimeters of penetration degrees
Embodiment 6
Step according to embodiment 1 prepares gel with HB-40, Santicizer 154 and composition thereof as thinner.Use 1.5 gram DDI and 10 gram Jeffamine T-5000 in each prescription, used diluent concentration is as shown in table 9.The electrical properties of the gel that makes so also is listed in table 9.
Embodiment 7
Step according to embodiment 1 prepares gel with polyfunctional polymeric polyisocyanate (Desmodur N-3300 derives from Mobay chemical company).Known this polymeric polyisocyanate is that the mixture reaction with excessive hexamethylene diisocyanate and diamines and triamine makes.The various composition as listed that the preparation gel is used are at table 10.The character of these gels is shown in table 11.
Table 10 is annotated a) Themninol 60; B) Shellflex 371; C) Santicizer 154; R) Therminol 66.
Embodiment 8
Having carried out an experiment compares with similar polyurethane gle and has improved heat aging performance to prove some polyurea gel.Used same thinner so that make the gel that makes have similar derivatized polymers and cross-linking density.Two kinds of polyurea gels of the embodiment of the invention are compared with two kinds of polyurethane gles of the non-embodiment of the invention.Listed the Voland hardness value of sample after keeping 7 days after the curing and in 100 ℃ baking oven of used prescription and each prescription in the table 12.Table 12 shows, two kinds of polyurethane gles surpass 75% and 85% respectively in the reduction of 100 ℃ of hardness after 7 days, but polyurea gel is only descending 39% and 11% through hardness after the same burin-in process.
In another experiment, prepared several stable gel of the present invention, be rich in isocyanic ester respectively, meet stoichiometric ratio and be rich in amine, but all identical in others.Gel is exposed under the oxygen in 225 ℃ in differential scanning calorimeter (DSC), need before the oxygen uptake fast elapsed time be respectively after measured＜14.5,16.1 and 19.6 minutes.Therefore, the gel that is rich in amine has much higher oxidative stability than other gel.
Table 12 is annotated:
Embodiment 9
Prepare the complexes of a cover listed component (all quantity and umber all refer to weight) preparation polyurea gel from table 13.Part A that various uses is used and B are placed in the disposable tube, are injected into the end that telephone cable or high-tension cable have been made joint through a static mixer/divider, make it solidify to form water seal.The gelation time of first kind of prescription is about 3 minutes, and gel hardness is 35 grams, and viscosity is 4 to 5 grams, and stress relaxation is 1.5%.The gelation time of second kind of prescription also is about 3 minutes, and gel hardness is 29 grams, viscosity 7.5 grams, stress relaxation 8.5%.About 2.5 minutes of the gelation time of the third prescription, hardness 28 grams, viscosity 25 grams, stress relaxation 7.0%.Last prescription is particularly suitable as stopping composition, for example is used in United States Patent (USP) 4,600, and 261,4,634,207,4,864,725,4,865,905,4,610, in 738 and 4,622, the 692 disclosed protectiveness goods; And be used in United States Patent (USP) 4,846,721,4,859,809 and 4,880,676 and the patent application EPO that announces, 298,713 and WO 89/08338 in the telephone terminal closure and electric wire and cable splice encapsulation object mentioned.Whole disclosures of all of the above patents and patent applications are all here quoted as a reference.
+: four (methylene radical 3-(3 ', 5 '-di-t-butyl-4 '-hydroxyphenyl) propionic ester) methane
*: 4,4 '-two (α, α-Er Jiajibianji) pentanoic
*: two (1,2,2,6,6-pentamethyl--4-piperidyl) sebate
Embodiment 10
This embodiment shows that can be less than 40% thinner with content prepares soft gel of the present invention.Gel is pressed the step preparation of embodiment 1.The character of used prescription and gained gel is shown in table 14.The viscosity value of these gels is high especially.
*Solidify 2 hours/60 ℃ under the room temperature, after 87 hours
Embodiment 11
Polyurea gel of the present invention is compared with non-polyurethane gle of the present invention, to evaluate them and to contain the consistency of about 22% dioctyl phthalate (DOP) as the plasticized polyvinyl chloride of softening agent.The prescription of polyureas and urethane (by weight) is listed in the following table 15.
The thick polyvinyl chloride (PVC) sheets of 25-30 mil (0.63-0.76 millimeter) is placed between 0.25 inch (6.3 millimeters) thick gel film, and subassembly kept 7 days at 80 ℃.Measure the variation of the changes in weight of polyvinyl chloride (PVC) sheets, anti-intensity and elongation at break then.Contact the polyvinyl chloride (PVC) sheets weightening finish 3% of placing with polyurea gel, its tensile strength of while almost constant (increasing by 1.5%), elongation at break reduces 20%.Contact the polyvinyl chloride (PVC) sheets of placing with polyurethane gle, its weight reduces 13.6%, and tensile strength increases by 18.8%, and elongation at break reduces 46%.
Embodiment 12
Step by embodiment 1 prepares a kind of polyurea gel with following component:
Part A: parts by weight part B: parts by weight
DDl??2.90??Sylvamide??125??2.00
Therminol??60??11.25??Therminol??60??11.25
Ketjenflex??8??11.25??Ketjenflex8??11.25
Silvamide 125 is the polymeric amide that are rich in acid amides that obtain from Sylvachem company.The hardness of gel is 34 grams, stress relaxation 14.5%, viscosity value 1 gram.
Fig. 1 has represented how the hardness of the curing polyurea gel of embodiment 1 becomes with polymer concentration and amount of diluent.Fig. 2 represents that how the hardness of these curing gels become with the ratio of diamines and triamine, and Fig. 3 has illustrated that then gelation time is how with the variation of the ratio of polymer concentration and diamines and triamine.
Claims (20)
1, a kind of composition that contains crosslinked polyureas, its Voland hardness are 1 to 500 gram, and elongation limit is at least 50%.
2, according to the composition of claim 1, wherein also contain thinner, the quantity of thinner is the crosslinked polyureas and the 25%(weight of thinner weight sum) to 95%(weight).
3, according to the composition of claim 1, wherein the molecular-weight average between the urea groups of polyureas is less than every moles of polymer 250 grams.
4, according to the composition of claim 1, wherein the molecular-weight average between the urea groups of polyureas is at least every moles of polymer 500 grams.
5, according to the composition of claim 1, wherein the molecular-weight average between the cross-link bond of polyureas is at least every mole 2000 gram.
6, according to the composition of claim 2, wherein the gel fraction of polyurea gel accounts for the 5%(weight of polyureas and thinner weight sum) to 75%(weight).
7, according to the composition of claim 2, wherein thinner contains two kinds of different thinners of specific inductivity.
8, a kind of compositions crosslinkable, its Voland hardness is 1 to 500 gram when fully solidifying, elongation limit is at least 50%, said composition contains first kind of organic compound of amino-contained, the second kind of organic compound that contains isocyanate group or isocyanic ester precursor group, and thinner, the quantity of thinner is the 25%(weight of first kind of organic compound, second kind of organic compound and thinner weight sum) to 95%(weight).
9, a kind of compositions crosslinkable according to Claim 8, wherein first kind of organic compound per molecule contains an average out to n amido, second kind of organic compound per molecule contains an average out to m isocyanate group or isocyanic ester precursor group, above-mentioned n and m all are at least 2, n and m sum are at least 4.1, said composition 25 ℃ gelation time less than 600 seconds.
10, composition according to Claim 8, wherein the chemical formula of first kind of organic compound is
The chemical formula of second kind of organic compound is
Wherein h, j, i and k can be identical or different, are to be at least 1 integer, and h, j, i and k sum are at least 20, but less than 200;
Each Q group is primary amine groups or the secondary amine that directly links to each other with A group carbon atom, can be identical or inequality;
Each P group is isocyanate group or the isocyanic ester precursor group that directly is connected with the carbon atom of A group, can be identical or different;
Each A group can be identical or different, and its chemical formula is:
Wherein each R group is alkylidene group, substituted alkylene, alkenylene, replacement alkenylene, arylidene or replaces arylidene, can be identical or different, and each R ' base is alkyl, substituted alkyl, aryl or substituted aryl, can be identical or different;
Each D group is a valence link or secondary amine, or alkylidene group, substituted alkylene, alkenylene, replacement alkenylene, arylidene or replacement arylidene, can be identical or different;
Each E group is a valence link or alkylidene group, substituted alkylene, alkenylene, replacement alkenylene, arylidene or replaces arylidene.
11, a cover comprises the complexes of two containers at least, and each container contains at least a material that is selected from in next group material:
(1) contains first kind of organic compound of amido;
(2) contain second kind of organic compound of isocyanate group or isocyanic ester precursor group;
(3) a kind of not with first kind of organic compound and second kind of inert diluent that organic compound reacts, the total amount of thinner is the 25%(weight of first and second kind organic compound and thinner weight sum in the container) to 95%(weight);
The distribution of above-mentioned substance in container, should make container under drying conditions when room temperature (25 ℃) is preserved 6 months, first kind of organic compound and second kind of organic compound are stable;
When the content of container mixes also fully curing, obtain crosslinked polyurea gel, its Voland hardness is 1 to 500 gram, elongation limit is at least 50%.
12, according to the complexes of claim 11, wherein first kind of organic compound per molecule contains an average out to n amido, and n is at least 2; Second kind of organic compound per molecule contains an average m isocyanate group or isocyanic ester precursor group, and wherein m is at least 2; N and m sum are at least 4.1.
13, according to the complexes of claim 11, wherein the chemical formula of first kind of organic compound is
The chemical formula of second kind of organic compound is
Wherein h, j, i and k are and are at least 1 integer, can be identical or different, and h, j, i and k sum are at least 20, but less than 200;
Each Q group is primary amine groups or the secondary amine that directly links to each other with A group carbon atom, can be identical or different;
Each P group is isocyanate group or the isocyanic ester precursor group that directly links to each other with A group carbon atom, can be identical or different;
Each A group can be identical or different, and its chemical formula is:
Wherein each R base is alkylidene group, substituted alkylene, alkenylene, replacement alkenylene, arylidene or replaces arylidene, can be identical or different; Each R ' base is alkyl, substituted alkyl, aryl or substituted aryl, can be identical or different;
Each D group is a valence link or secondary amine, or alkylidene group, substituted alkylene, alkenylene, replacement alkenylene, arylidene or replacement arylidene, can be identical or different;
Each E group is a valence link or alkylidene group, substituted alkylene, alkenylene, replacement alkenylene, arylidene or replacement arylidene, can be identical or different.
14, according to the complexes of claim 11, first kind of end capped polyoxypropylene of alpha-amino group propyl group, omega-amino-that organic compound is a molecular weight from 200 to 20000 wherein; The end capped polyoxyethylene of alpha-amino group ethyl, omega-amino-of molecular weight from 200 to 20000; The end capped polyoxy butylene of alpha-amino group ethyl, the omega-amino-of molecular weight from 250 to 25000; 4,4 '-diamino-3,3 '-the dimethyl dicyclohexyl methyl hydride; Diethyl toluene diamine; 3,5-diformazan sulfenyl-2,4-tolylene diamine; The end capped polydimethylsiloxane of aminopropyl dimethyl of molecular weight from 2000 to 30000; The end capped polydimethylsiloxane of amino butyl dimethyl of molecular weight from 2000 to 30000; The diamines dimer; Be rich in the polyamide resin of amine; End capped amine-the epoxy adduct of amine; Diaminodiphenylsulfone(DDS); Ethylene aniline; Methylene dianiline (MDA); Diethyl toluene diamine; 3,5-diformazan sulfenyl-2,4-tolylene diamine; The end capped polyhutadiene of amine; The end capped perbutan of amine; Or any two or more mixture in these materials.
15, according to the complexes of claim 11, wherein second kind of organic compound is ethylidene diisocyanate; Trimethylene diisocyanate; Ten dimethylene diisocyanates; Hexamethylene diisocyanate; Hexamethylene diisocyanate trimer; Four ethylidene diisocyanates; Pentamethylene diisocyanate; Propylidene-1, the 2-vulcabond; 2,3-dimethyl tetramethylene diisocyanate; 1,4-two isocyanato-hexanaphthenes, methyl hexamethylene diisocyanate; 3-isocyanato-methyl-3,5,5-3-methyl cyclohexanol based isocyanate; Cyclopentenes-1, the 3-vulcabond; To phenylene vulcabond; Naphthalene diisocyanate ester; 4,4 '-the diphenylene methane vulcabond; 4,4 '-diphenylene propane vulcabond; The tetramethyl-eylylene diisocyanate; 1,2,3,4-four isocyanato-butane; Butane-1,2, the 3-triisocyanate; Contain the aliphatic series and the aromatic polyether of the linearity and the branching of isocyanic ester, or contain the aliphatic series and the aromatic polyester of the linearity and the branching of isocyanic ester.
16, a kind of method that forms polyurea gel, the Voland hardness of formed gel are 1 to 500 gram, and elongation limit is at least 50%, and this method is included under the inert diluent existence following material one is reacted
(1) first of amino-contained kind of organic compound; With
(2) contain second kind of organic compound of isocyanate group or isocyanic ester precursor group;
Described thinner not with first kind of organic compound or second kind of organic compound reaction, its quantity is the weight of 25%(at least of first kind of organic compound, second kind of organic compound and thinner weight sum) to 95%(weight).
17, the method at the bottom of a kind of protecting group is included in the substrate cast and contains following mixture of ingredients and make mixture solidified:
(1) first of amino-contained kind of organic compound;
(2) contain second kind of organic compound of isocyanate group or isocyanic ester precursor group;
(3) a kind of thinner, it does not react with first kind and second kind of organic compound, its quantity is 25%(weight at least) to 95%(weight).
18, according to the method at the bottom of the protecting group of claim 13, wherein mixture is less than 900 seconds 25 ℃ gelation time.
19, the method at the bottom of a kind of protecting group comprises:
(1) prepare a kind of composition that contains crosslinked polyureas, the Voland hardness of this composition is from 1 to 500 gram, and elongation limit is at least 50%;
(2) composition is applied to matrix.
20, a kind of preparation has the method for compositions of predetermined specific inductivity, comprising:
(A) select a kind of thinner adulterant, the specific inductivity of each thinner is all different with selected all other thinners, selects the weight ratio of each thinner, makes adulterant have desired specific inductivity;
(B) adulterant is added in the composition that contains crosslinked polyurea gel, the quantity of adulterant should make composition have desired dielectric constant values.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US48568690A | 1990-02-27 | 1990-02-27 | |
| US485,686 | 1990-02-27 |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95106211 Division CN1114973A (en) | 1990-02-27 | 1995-05-24 | Polyurea gel compositions and article therefrom |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1054433A true CN1054433A (en) | 1991-09-11 |
Family
ID=23929074
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 91101217 Withdrawn CN1054433A (en) | 1990-02-27 | 1991-02-27 | Polyurea gel compositions and goods thereof |
| CN 95106211 Withdrawn CN1114973A (en) | 1990-02-27 | 1995-05-24 | Polyurea gel compositions and article therefrom |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 95106211 Withdrawn CN1114973A (en) | 1990-02-27 | 1995-05-24 | Polyurea gel compositions and article therefrom |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0517843A1 (en) |
| JP (1) | JPH05503549A (en) |
| CN (2) | CN1054433A (en) |
| AU (1) | AU644985B2 (en) |
| CA (1) | CA2076866A1 (en) |
| NZ (1) | NZ237054A (en) |
| WO (1) | WO1991013109A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104633281A (en) * | 2015-02-05 | 2015-05-20 | 山东远利华矿用装备有限公司 | Composite type ant-flaming anti-static polyurea polymer cable supporting hook |
| CN107488254A (en) * | 2017-08-29 | 2017-12-19 | 北京石油化工学院 | Dielectric elastomer material and preparation method thereof |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5529508A (en) * | 1994-04-01 | 1996-06-25 | Raychem Corporation | Sealing member |
| WO1998014519A1 (en) | 1996-10-01 | 1998-04-09 | Nippon Zeon Co., Ltd. | Dispersed polymer composition |
| KR101832504B1 (en) * | 2009-06-29 | 2018-02-26 | 바스프 에스이 | Porous gels based on aromatic polyurea |
| JP5741249B2 (en) * | 2011-06-27 | 2015-07-01 | Jsr株式会社 | Photocurable composition and cured film thereof |
| CN110172861B (en) * | 2019-05-16 | 2021-10-22 | 浙江恒达新材料股份有限公司 | Chlorine-free wet strength agent and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3325346A (en) * | 1964-06-26 | 1967-06-13 | Chemirad Corp | Process of making paper using reaction product of polyethyleneimine and polyisocyanate |
| DE1595748A1 (en) * | 1965-06-01 | 1970-05-14 | Gen Mills Inc | Polyisocyanate and polyamine compounds hardening due to the action of moisture |
| US3892696A (en) * | 1972-05-12 | 1975-07-01 | Grace W R & Co | Polyureas and preparation thereof |
| MX170643B (en) * | 1986-08-01 | 1993-04-12 | Ici America Inc | POLYUREAS PREPARED FROM A MIXTURE OF POLYAMINS AND A POLYISOCYANATE |
-
1991
- 1991-02-08 NZ NZ23705491A patent/NZ237054A/en unknown
- 1991-02-25 WO PCT/US1991/001266 patent/WO1991013109A1/en not_active Application Discontinuation
- 1991-02-25 EP EP19910906322 patent/EP0517843A1/en not_active Withdrawn
- 1991-02-25 CA CA 2076866 patent/CA2076866A1/en not_active Abandoned
- 1991-02-25 JP JP50604191A patent/JPH05503549A/en active Pending
- 1991-02-25 AU AU74791/91A patent/AU644985B2/en not_active Ceased
- 1991-02-27 CN CN 91101217 patent/CN1054433A/en not_active Withdrawn
-
1995
- 1995-05-24 CN CN 95106211 patent/CN1114973A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104633281A (en) * | 2015-02-05 | 2015-05-20 | 山东远利华矿用装备有限公司 | Composite type ant-flaming anti-static polyurea polymer cable supporting hook |
| CN107488254A (en) * | 2017-08-29 | 2017-12-19 | 北京石油化工学院 | Dielectric elastomer material and preparation method thereof |
| CN107488254B (en) * | 2017-08-29 | 2019-12-20 | 北京石油化工学院 | Dielectric elastomer material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| NZ237054A (en) | 1993-03-26 |
| AU7479191A (en) | 1991-09-18 |
| CN1114973A (en) | 1996-01-17 |
| WO1991013109A1 (en) | 1991-09-05 |
| CA2076866A1 (en) | 1991-08-28 |
| AU644985B2 (en) | 1993-12-23 |
| JPH05503549A (en) | 1993-06-10 |
| EP0517843A1 (en) | 1992-12-16 |
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| SE01 | Entry into force of request for substantive examination | ||
| C03 | Withdrawal of patent application (patent law 1993) | ||
| WW01 | Invention patent application withdrawn after publication |