CN1086241A - Quick-set non-cementitious adhesive - Google Patents
Quick-set non-cementitious adhesive Download PDFInfo
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- CN1086241A CN1086241A CN93118774A CN93118774A CN1086241A CN 1086241 A CN1086241 A CN 1086241A CN 93118774 A CN93118774 A CN 93118774A CN 93118774 A CN93118774 A CN 93118774A CN 1086241 A CN1086241 A CN 1086241A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J121/00—Adhesives based on unspecified rubbers
- C09J121/02—Latex
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J201/00—Adhesives based on unspecified macromolecular compounds
- C09J201/02—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C09J201/025—Adhesives based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing nitrogen atoms
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Abstract
The present invention also provides a kind of method of improving non-cementaceous binding agent initial stage cohesive bonding intensity under all conditions of cure by a kind of aqueous quick-set non-cementitious composition is provided.
Description
A kind of moisture quick-set non-cementitious adhesive ， And of tack and cohesive strength that provides is provided relates to the tack of non-cementaceous binding agent and improving one's methods of cohesive strength.
Outside isolation (heat, sound) and facing system (" EIFS ") are mounted in the MULTILAYER COMPOSITE system on buildings and other outdoor structural outer surface, play isolation (heat, sound), the effect of protecting and beautifying.The outside surface of buildings or other outdoor structure can be by concrete, slag brick, stone, brick, timber, formations such as plasterboard.Multiple the coating at the outside surface ， of buildings or other outdoor structure And of layer of material a kind ofly coated a kind of finishing coat again with silk screen enhanced undercoat, above-mentioned this layer material generally be solid or the sheet-form of foaming such as polystyrene foaming and that extrude.If do not adopt mechanical fastening system, then need this layer material to be adhered on the outside surface of buildings or other outdoor structure with a kind of binding agent.This binding agent can contain cement, also can not contain cement.The cement binding agent that still do not contain cement all encounters problems.
Calcium oxide, silica, aluminum oxide and ferric oxide at high temperature are combined to a kind of compound material of water cement in suitable ratio.When water cement contacts with water, its component begins the general mistake of Shui He And and was solidified into hard material in 1～3 hour.This applies just for the binding agent that contains cement when they remain fluid and only stays short working life.Employing contains the contractor of cement binding agent because adhesive cures just can not be used (generally less than about 5 hours) after becoming hard material, must throw away any still untapped material.This causes very big waste.
Adopt the non-cementaceous binding agent problem that can avoid waste.But traditional non-cementaceous binding agent has run into the problem of tack and first cohesive bonding difference owing to lack by cohesiveness and cohesive strength that cement provided.Depend on that envrionment conditions can be some days its time of drying.In addition since the topped material on buildings or other outdoor structural outer surface of this layer generally be hydrophobic material such as the foamed polystyrene body, this material hinders water to run out from the outside facing of stratiform system, thereby makes this problem more become serious.Till the outside facing of stratiform system solidified, sticking knot agent And does not have enough cohesive bondings made material layer mutually bonding with the outside surface of buildings or other outdoor structure with cohesive strength.May rupture or be cold and the humid region at material, problem recited above is especially outstanding.
The purpose of this invention is to provide a kind of non-cementaceous adhesive composition, said composition is easy to apply ， And and tack and cohesive strength are provided under all conditions of cure and do not stay waste.
Another purpose of the present invention provides a kind of method of improving tack and cohesive strength under non-all conditions of cure of cementaceous binding agent.
The present invention moisturely fast do non-cementitious composition and has solved the problem that traditional cementaceous and non-cementitious composition are run into by providing a kind of, and said composition is easy to coating, can improve tack and cohesive strength and do not stay waste under all conditions of cure.The present invention is specially adapted to do outside isolation (heat, sound) and facing system caking agent.The present invention also provides a kind of method of improving tack and cohesive bonding intensity under all conditions of cure of non-cementaceous binding agent.
Moisture fast dried non-cementitious composition of the present invention needs three kinds of components:
(1) has a kind of film forming latex polymer of anion characteristic;
(2) by 20%(weight at least) contain a kind of amine-containing polymer that the amine functional group monomer constitutes, and
(3) a kind of volatile alkali.
The method of improving tack and cohesive bonding intensity under all conditions of cure comprises:
(1) make a kind of non-cementaceous binding agent that contains following component:
(a) a kind of film forming latex polymer with anion characteristic;
(b) a kind of polymkeric substance that contains amine; And
(c) a kind of volatile alkali;
(2) non-cementaceous binding agent is coated in the outside surface of buildings or other outdoor structure;
(3) solid or foam stratiform protecting materials are compound on the non-cementaceous binding agent.
Aqueous binders composition of the present invention needs:
(1) a kind of film forming latex polymer with anion characteristic;
(2) a kind of polymkeric substance that contains amine; And
(3) a kind of evaporable alkali.
Aqueous adhesive composition of the present invention is " a non-cementaceous ", and this title used herein refers to this composition and do not contain cement fully.
Aqueous adhesive composition of the present invention provides tack and cohesive bonding intensity under all conditions of cure.Title used herein " initial stage " refers to the period that binding agent still wets.Title used herein " cohesive bonding intensity " refers to the magnetism that has between the binder material itself." cohesive strength " refers to magnetism that binder material deposits the matrix tool and the intensity that is bonded together with matrix surface.The harshest condition of cure of aqueous adhesive composition of the present invention is cold and moist environment.
" second-order transition temperature " or " Tg " is meant the glass transition temperature of polymer that calculates by Fox equation (1,3 page of Bulletin of American Physics Society, 123(1956)) here:
1/(Tg) = (W
1)/(Tg(1)) (W
2)/(Tg(2))
Concerning a kind of multipolymer, W
1And W
2Refer to the weight fraction of two kinds of comonomers, Tg(1) and Tg(2) refer to the second-order transition temperature of the homopolymer of two kinds of correspondences.
Aqueous binders composition of the present invention needs a kind of film forming latex polymer with anion characteristic.Here used title " latex " refers to a kind of insoluble polymer that can make by traditional polymerization process such as letex polymerization.This latex polymer is to be made by any monomer or the monomer mixture that can generate the water-insoluble latex polymer, and this polymkeric substance is film forming under the coating condition.
The Tg of latex polymer is limited by the concrete purposes of employed adhesive composition only.For example, if this binding agent in outdoor use in summer of sweltering heat, then the optional Tg that makes it that selects of latex polymerization compositions is higher than this binding agent at the selected Tg of outdoor use in the winter of cold.In general, the Tg of latex polymer is-50 ℃～about 50 ℃ approximately.The coating of latex polymer that contains Tg＜-50 ℃ is generally inapplicable, because its Tai Ruan And lacks the enough intensity as binding agent.The coating of latex polymer that contains Tg＞50 ℃ is generally also inapplicable, because it is difficult to very much film forming, even be higher than room temperature.Preferably Tg is about-15 ℃～about 10 ℃ polymkeric substance.Most preferably Tg is about-10 ℃～about 5 ℃ polymkeric substance.
The present invention also can adopt the more complicated polymkeric substance of form to be implemented such as the core-shell-type polymkeric substance.These complicated polymer morphologies usually show a plurality of Tg, and one of its a plurality of Tg can demonstrate and exceed the Tg value of-50 ℃～about 50 ℃ of scopes approximately, but average or effective Tg of polymkeric substance must be-50 ℃～about 50 ℃ of pacts.
The anion characteristic of film forming latex polymer obtains by arbitrary different methods, and the most frequently used method is to adopt anion surfactant or dispersion agent used as stabilizers during the letex polymerization or after polymerization finishes it is being added into emulsion.During the stable latex polymerization of these negatively charged ion or after the polymerization, also can contain nonionic surface active agent in the latex.What tensio-active agent and dispersion agent wherein share is the salt of aliphatics rosin and naphthenic acid; the lower molecular weight condensation product of naphthene sulfonic acid and formaldehyde; suitable hydrophilic-hydrophobic equilibrated carboxylic acid polyalcohol and multipolymer; higher alkyl sulfates (such as sodium lauryl sulphate); alkylaryl sulphonate is (such as dodecylbenzene sulfonate; isopropyl benzene sodium sulfonate or potassium or isopropyl naphthalene sodium sulfonate or potassium); thio succinate is such as dioctyl sulfo-sodium succinate; senior alkyl sulfo-succsinic acid an alkali metal salt (as the octylsulfo sodium succinate); N-methyl-N-hexadecanoyl Sodium taurine salt; the oil base hydroxyethyl sulfonate; the an alkali metal salt of alkylaryl multi-ethoxyl alcohol sulfuric acid (or sulfonic acid) (as containing 1～5 the unitary uncle's Octylphenoxy of oxyethylene group-many ethoxyethyl groups sodium sulfate), and technical crowd various other anion surfactants and the dispersion agent known.
Another kind of latex polymer with anion characteristic, its anion characteristic are to get owing to result that polymkeric substance contains a small amount of acidic group, and acidic group can be in the form of salt such as alkali metal salts or ammonium salt.The example of this class acidic group can be from the initiator fragment that adds, toxilic acid, vinyl sulfonic acid, Ba Dousuan, vinylformic acid, methacrylic acid, methylene-succinic acid etc.
The latex polymer with anion characteristic that the 3rd class is share is a kind of containing through the monomeric latex polymer of neutral alkalescence, this class monomer such as acrylamide, Methacrylamide etc.
This latex polymer can have more than one type anion characteristic.
Latex polymer with anion characteristic can be by known step preparation, the visible textbook of publishing of content, exercise question is as Emulsion Polymerization:Theory and Practice(author: D.C.Blackley, Wiley company published in 1975), Emulsion Polymerization(author: F.A.Bovey etc., Interscienel Publishers company publishes nineteen sixty-five).This latex polymer is generally polymkeric substance or the multipolymer that is made by following monomer, these monomers such as methyl acrylate, ethyl propenoate, butyl acrylate, 2-EHA, decyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, vinylbenzene, divinyl, ethene, vinyl acetate, (this acid contains C for chain length to the vinyl ester of " Versatic " acid
9, C
10And C
11Uncle's monocarboxylic acid, its vinyl ester is also referred to as " Vinyl Versatate "), vinylchlorid, vinyl pyridine, vinylidene chloride, vinyl cyanide, chloroprene, vinylformic acid, methacrylic acid, methylene-succinic acid, toxilic acid and fumaric acid.That preferably adopt is α, the polymkeric substance of β-ethylenically unsaturated monomer and ester thereof and multipolymer (the especially polymkeric substance of acrylate and methacrylic ester and multipolymer).They should be produced by the method that hereinafter provides, and introduce this article here for your guidance: " Emulsion Polymerization of Acrylic Monomers:May, 1966 ", Rohm ﹠amp; (Philadelphia Pennsylvania) publishes in Haas company.
Aqueous binders of the present invention needs a kind of polymkeric substance that contains amine, and this polymkeric substance is by 20%(weight at least) monomer that contains amine functional group makes.Preferably polymkeric substance contains 50%(weight at least) contain the monomer of amine functional group.This molecular-weight average water-soluble or the water dispersible amine-containing polymer also is preferably about 5000～about 100,000.
The monomeric example that contains amine functional group comprises as follows:
1. aminoalkyl vinyl ether or thioether, wherein alkyl can be that straight or branched Xing ， And contains 2～3 carbon atoms, wherein nitrogen-atoms can be the primary, the second month in a season or tertiary N atom (U.S.2,879,178).Under the back kind situation, one of remaining hydrogen atom can be by alkyl, and hydroxyalkyl or alkoxyalkyl replace, and its alkyl component can contain 1～4 carbon atom, preferably only contains a carbon atom.
Object lesson comprises: β-aminoethyl vinyl ether; β-aminoethyl vinyl thioether; N-monomethyl-β-aminoethyl vinyl ether or thioether; Single ethyl-the β of N--aminoethyl vinyl ether or thioether; N-monobutyl-β-aminoethyl vinyl ether or thioether; And N-monomethyl-3-aminopropyl vinyl ether or thioether.
2. acrylamide or acrylate, all suc as formula shown in the II:
In the formula:
R is H or CH
3;
N is 0 or 1;
X is O or N(H);
When n is 0, A is O(CH
2) in the x(formula x be 2-3) or (O-alkylidene group) y(formula in (O-alkylidene group) y be polyoxyalkylenes, its molecular weight is 88～348, wherein each alkylidene group can be identical or different, and can be ethylidene or propylidene);
When n is 1, A is the alkylidene group that contains 2-4 carbon atom;
R
*Be H, methyl or ethyl;
R is H, methyl or ethyl;
R
0Be H, phenyl, benzyl, methyl-benzyl, cyclohexyl or (C
1-C
6) alkyl.
The example of formula II compound comprises: the dimethylaminoethyl of acrylic or methacrylic acid; The β of acrylic or methacrylic acid-ammonia ethyl ester; The acrylamide of N-β-aminoethyl or Methacrylamide; The single methylamino-ethyl of N-() acrylamide or Methacrylamide; N-(list-the normal-butyl of acrylic or methacrylic acid)-4-ammonia butyl ester; The methacryloxypropyl ethoxy ethyl amine; And acryloyl-oxy propoxypropylamine.
3.N-acryloyloxyalkyl-oxazolidines and N-acrylic acid alkyl-tetrahydrochysene-1,3-oxazine and corresponding component, in these components, alkyl bond alkoxy alkyl and poly-(alkoxyalkyl) replace, and all these compounds all comprise with the formula III:
In the formula:
R is H or CH
3;
M is the integer of 2-3;
R ', when not with R
2When directly linking to each other, can be selected from H, phenyl, benzyl, and (C
1-C
12) alkyl;
R
2, when directly not linking to each other, can be selected from H with R ', and (C
1-C
4) alkyl;
R
1And R
2, when directly connecting together, when going up the banded carbon atom and form the 5-6 carboatomic ring with ring in the formula, i.e. R
1And R
2When connecting together, can be selected from pentamethylene and tetramethylene;
A
1Be O(CmH
2M)-or (O-alkylidene group) n, wherein (O-alkylidene group) n is a polyoxyalkylenes, and its molecular weight is 88～348, and each alkylidene group can be identical or different in this formula, and can be ethylidene or propylidene.
The compound of formula III can be hydrolyzed into secondary amine under various conditions.The product of hydrolysis production IV:
The compound of formula III is disclosed in the U.S.3 of commonly-assigned us, and 037,006 and 3,502,627, and in their corresponding foreign application books and the patent, wherein disclosed any monomeric compound all can be used to make the used multipolymer of the present composition.
The example of formula III compound comprises:
Oxazolidinylethyl methacrylate;
Bing Xi Suan oxazolidinyl ethyl ester;
3-(γ-methacrylic acid propyl group)-and tetrahydrochysene-1, the 3-oxazine;
3-(Beta-methyl vinylformic acid ethyl)-2,2-Wu Ya Jia Ji oxazolidine;
3-(Beta-methyl vinylformic acid ethyl)-the fast azoles alkane of 2-methyl-2-propyl group;
N-2-(2-vinylformic acid oxyethyl group) Yi Ji oxazolidine;
N-2-(2-methacrylic acid oxyethyl group) Yi Ji oxazolidine;
N-2-(2-methacrylic acid oxyethyl group) ethyl-5-methyl-oxazolidines;
N-2-(2-vinylformic acid oxyethyl group) ethyl-5-methyl-oxazolidines;
3-(2-(2-methacrylic acid oxyethyl group) ethyl))-2,2-Wu Ya Jia Ji oxazolidine;
3-(2-(2-methacrylic acid oxyethyl group) ethyl)) 2,2-Er Jia Ji oxazolidine;
3-(2-(methacrylic acid oxyethyl group) ethyl)-2-Ben Ji oxazolidine.
4. the polymer of monomers that easily produces amine by hydrolysis can be used as containing amine component or being used for producing and containing the amine component polymkeric substance of this adhesive composition.The monomeric example of this class is vinylformic acid ketoimine and vinylformic acid-aldimine, and its formula V and VI are as follows:
In the formula,
R is H or CH
3;
Q is selected from following group:
R
6Be H, or at a CHR
6It can be a methyl in the unit;
R
5Be selected from (C
1-C
12) alkyl and cyclohexyl;
R
4Be selected from (C
1-C
12) alkyl and cyclohexyl;
R
3Be selected from phenyl, halobenzene base, (C
1-C
12) alkyl, cyclohexyl, and (C
1-C
4Alkoxyl phenyl;
A " is (C
1-C
12) alkylidene group;
A
o, B and D are identical or different oxyalkylene group, its general formula is
-OCH(R
7)-CH(R
7), R in the formula
7Be H, CH
3, or C
2H
5;
X is the integer of 4-5;
n
0Integer for 1-200;
n
1Integer for 1-200;
N " be the integer of 1-200, n
0-1, n
1-1 and n " 1 summation is 2-200.
The illustrative compound of formula V and VI is:
Methacrylic acid 2-(4-(2, the inferior heptyl of 6-dimethyl) amino) ethyl ester;
Methacrylic acid 3-(2-(4-methyl pentylidene) amino) propyl ester;
Methacrylic acid β-(benzal amino) ethyl ester;
Methacrylic acid 3-(2-(4-methyl pentylidene) amino) ethyl ester;
Vinylformic acid 2-(4-(2, the inferior heptyl of 6-dimethyl) amino) ethyl ester;
Methacrylic acid 12-(ring pentylidene amino) dodecane ester;
N-(1,3-dimethyl butylidene)-2-(2-methacrylic acid oxyethyl group) ethamine;
The N-(benzylidene) methacrylic acid ethoxy ethyl amine;
N-(1,3-dimethyl butylidene)-2-(2-vinylformic acid oxyethyl group) ethamine;
The N-(benzylidene)-and 2-(2-vinylformic acid oxyethyl group) ethamine.
Formula V and VI compound be in acidity, and hydrolysis in neutrality or the alkaline aqueous medium generates corresponding primary amines or its salt, during hydrolysis following formula-the N=Q base becomes-NH
2And O=Q.United States Patent (USP) 3,037,969 and 3,497,485 disclose the compound of formula V and VI, and wherein disclosed any monomeric compound all can be used to make the used multipolymer of water-soluble polymers part in the present composition.
The class amine-containing polymer that the present invention preferably uses is water miscible.No matter so-called water-soluble this polymkeric substance that refers to be in free alkali, and the state of neutrality or salt all is complete solubility.Preferably this solubility all possesses when all PH, especially in about 4～10 scope.The little satisfied water-soluble amine-containing polymer of a class is insoluble when high pH value usually, and just at acid pH value, especially PH is only solvable or the part solubility in about scope of 4～about 7.The so-called partly soluble two kinds of situations that are meant, a kind of situation is the polymer moieties water soluble, another situation is aggregate (being generally by water height swollen aggregate) the state dissolving with micella state or individual molecule of all polymkeric substance.Back kind situation often is called colloidal solution.Preferably the major part of polymkeric substance is soluble when acid pH value.Water-soluble amine-containing polymer of the present invention had both comprised the polymkeric substance of complete solubility, described just now part soluble polymer above also comprising.
That one class is share but still not quite satisfied amine-containing polymer is an insoluble polymer, and as described below, its molecular weight is equivalent to the low side of its water-soluble counterpart scope.These water-insoluble amine-containing polymers play the same of water-soluble polymers.When replacing water-soluble polymerss, improved the initial adhesive strength of the stable latex polymer of negatively charged ion with these insoluble polymers; But, this improvement do not resemble usually reach with water-soluble polymers obvious.
In general, above-mentioned 1,2,3 and 4 class monomers account for 20%(weight at least) amine-containing polymer can produce by solution polymerization in water medium, medium can be neutral, and is alkaline or acid, depends on the polymkeric substance of specifically seeking.Polymerization is carried out in containing the water medium of small amount of acid usually, and this acid can be organic acid or mineral acid such as acetic acid or hydrochloric acid.This amine-containing polymer comprise contain the most nearly 80%(weight) one or more following monomeric multipolymers, these monomers are such as methyl acrylate, acrylamide, Methacrylamide, and the quaternary amine such as the chlorination 2-methacrylic acid ethyl trimethyl ammonium that get by amine monomers.Also can use and say relatively that on a small quantity insoluble comonomer makes water-soluble polymers.Insoluble polymer can contain relatively large following comonomer.This class monomer comprises as band (C
1-C
18) pure acrylate and band (C
1-C
18) pure methacrylic ester, particularly band (C
1-C
4) the above-mentioned ester of alkanol; Vinylbenzene, Vinyl toluene, vinyl acetate, vinylchlorid, vinylidene chloride, the vinylbenzene of replacement, divinyl, the divinyl of replacement, ethene; And vinyl cyanide and acrylamide or methacrylonitrile and Methacrylamide.Used concrete comonomer (one or more) depends on the ratio of making used amine-containing monomer in this multipolymer in making given amine-containing polymer.Preferably only using has the comonomer of higher solubility to make water-soluble polymers in water.Therefore this base polymer is anionic and optional non-ionic vinyl polymer of monomers or multipolymer.The example of cationic monomer is an amine, imines and quaternary amine; Other monomer of enumerating is a non-ionic type.Therefore, these water solubility copolymers are except because of the impurity in the used monomer or synthetic, store or use in have a little hydrolysis to exist micro-acidic group do not contain acidic group outward.
The viscosity-average molecular weight of insoluble amine-containing polymer is about 5000～about 100,000, preferably about 15,000～about 90,000.The molecular weight of water-soluble polymers can drop on very wide scope; In general, viscosity-average molecular weight is about 5,000～about 300,000, preferably about 40,000～about 100,000.The consumption of amine-containing polymer can account for about 0.1%～about 20%(weight of anionic latex polymkeric substance and amine-containing polymer gross weight), preferred range is 0.5～8%.
Water-soluble amine-containing polymer had both comprised that completely soluble polymkeric substance also comprised partly soluble polymkeric substance.What the name of water-soluble amine-containing polymer was said the name of sth. is at free alkali, all completely soluble polymkeric substance of neutrality or salt state.Some polymkeric substance is all solvable at all PH, and other are then solvable between 5～10 according to appointment a PH scope.Other amine-containing polymer is generally insoluble and at acid pH value, especially PH is about scope of 5～about 7 when high PH, and is then solvable or part is solvable.So-called part is solvable to be meant two kinds of situations, and a kind of situation is the polymer moieties water soluble, and another kind of situation is aggregate (being generally by water height swollen aggregate) the state dissolving with micella state or individual molecule of all polymkeric substance.Back kind situation often is called colloidal solution.Preferably, the major part of polymkeric substance is soluble when acid pH value.
In general, the polymkeric substance that contains amine can be produced by solution polymerization in water medium, and medium can be neutral, alkaline or acid, depends on the polymkeric substance of specifically seeking, and this is that the crowd knows technically, for example referring to U.S.4, and 119,600.Polymerization is carried out in containing the water medium of small amount of acid usually.This acid can be organic acid or mineral acid such as acetic acid or hydrochloric acid.This amine-containing polymer comprise contain the most nearly 80%(weight) one or more monoene belong to multipolymer, these monomers such as methyl acrylate, acrylamide and the Methacrylamide of unsaturated monomer.Also can use and say relatively that on a small quantity insoluble comonomer makes water-soluble polymers.Insoluble polymer can contain relatively large following comonomer, and this class monomer comprises as band (C
1-C
18) pure acrylate and band (C
1-C
18) pure methacrylic ester, particularly band (C
1-C
4) the above-mentioned ester of alkanol; Vinylbenzene, Vinyl toluene, vinyl acetate, vinylchlorid, vinylidene chloride, the vinylbenzene of replacement, divinyl, the divinyl of replacement, ethene; And vinyl cyanide and acrylamide or methacrylonitrile and Methacrylamide.Used concrete comonomer (one or more) depends on the ratio of making used amine-containing monomer in this multipolymer in making given amine-containing polymer.Therefore this base polymer is anionic and optional non-ionic vinyl polymer of monomers or multipolymer.The monomeric example of anionic is amine and imines; Other monomer of enumerating is a non-ionic type.Therefore, these water solubility copolymers are except because of the impurity in the used monomer or synthetic, store or use in have a little hydrolysis to exist micro-acidic group do not contain acidic group outward.
Adhesive composition of the present invention needs a kind of volatile alkali.The type of used volatile alkali and consumption must be enough to make the PH of composition to be elevated to the amine functional group of amine-containing polymer by the degree of nonionicization (deprotonation), generally being elevated at least, PH is 5, be preferably PH=7～9, to avoid with negatively charged ion in the binder composition stable latex polymer and the interaction of other anionic group.
Reach the consumption estimation of the volatile alkali that this degree needs, its starting point can from and all acidic group in the latex (promptly from the band carboxylic monomer of copolymerization; Tensio-active agent; Or the acidic group of initiator) and the equivalents of the alkali that needs of the conjugate acid of amine calculate.If amine is not filled a part deprotonation, latex can demonstrate observable unstable sign in time, raises microscopically observable " particle rafting ", the gathering/pectisation at a kind of initial stage such as viscosity.Usually, be enough to produce stable system, though possible the higher volatile alkali of content (～3～4 equivalent) must be arranged for standing storage is stable with the volatile alkali of monovalent (calculating) according to the acid of latex and the titre of polyamine.Only otherwise depart from aim of the present invention and can adopt the more alkali of volume, but this can influence coating " fast doing " performance.If used in process of production device is gone into any operation in the sealed vessel from adding volatile alkali up to the packing of product, exist the chance of volatile alkali evaporation, the consumption that then should improve the volatile amine that adds production equipment is to recover damage.
After the binding agent coating, the volatile alkali evaporation reduces the PH of composition.Begin protonated degree takes place when this PH is reduced to amine functional group, amine functional group becomes anionic property.It is believed that fast dried be because amine functional group changes into the negatively charged ion state in the presence of the stable latex polymer of negatively charged ion produce, but the generation quick-drying really cutter manage and do not make clear as yet, this Ren of inventor And does not wish to be subjected to the theory of exact mechanism to fetter.
The volatile alkali that is suitable for includes but not limited to amine, morpholine, alkylamine, 2-methylethylolamine, N-methylmorpholine, quadrol, and their mixture.What preferably use is ammonia.
Moisture fast dried non-cementaceous caking agent can randomly contain a kind of metal ion that is in, salt, the water-soluble or water dispersible polyvalent metal of complex compound or oxide compound state.The polyvalent metal ion that can adopt is such as calcium, magnesium, zinc, barium, strontium, aluminium etc.Also can adopt the complex compound of polyvalent metal ion, such as six ammino zinc, bicarbonate of ammonia zinc etc., and the polyvalent metal ion salt of band counter ion, such as muriate, acetate, supercarbonate etc.Preferred polyvalent metal is a zinc.
Polyvalent metal ion, salt, the dosage of complex compound or oxide compound account for about 0.5～about 10%(weight of latex polymer solid weight).Preferred consumption is about 1～about 7%(weight).
In addition, the present invention can adopt traditional binder component such as pigment, and tackiness agent connects material, extender, dispersion agent, tensio-active agent, coalescing agent, wetting agent, rheology modifiers, thickening material, drying inhibitor, defoamer, tinting material, wax, sanitas, thermo-stabilizer, solvent, anti, siccative etc.
When the type of selecting additive and consumption, must be especially careful, to avoid the making PH of composition change to the degree that influences its stability in storage, or avoid making PH to be buffered to such degree, so that PH And does not drop to the protonated numerical value that is enough to take place polyamine after coating.For example, can prolong to such an extent that make us being difficult to accepting the set time of the binding agent that makes as filler of the lime carbonate that adopts lower polyamine of PKa and too many amount.
Adhesive composition of the present invention, its solid content are generally about 10%～about 75%(weight), viscosity is that about 50,000 centipoises are to about 300,000 centipoises.
Adhesive composition of the present invention is applicable to the adhesive for building purposes that needs tack and cohesive bonding intensity of any kind, such as EIFS; The fornix bottom; Comprise vinyl plastics matter, pottery and xyloid floor tile, glued board etc.
Method of the present invention can be used for improving the initial stage cohesive bonding intensity of non-cementaceous binding agent, and this method comprises:
(1) make a kind of non-cementaceous binding agent that contains following component:
(a) a kind of film forming latex polymer with anion characteristic;
(b) by 20%(weight at least) contain a kind of polymkeric substance that contains amine that the amine functional group monomer constitutes; And
(c) a kind of volatile alkali;
(2) non-cementaceous binding agent is coated in the outside surface of buildings or other outdoor structure;
(3) solid or foam stratiform protecting materials are compound on the non-cementaceous binding agent.
Buildings and other outdoor structure can be by concrete, cement, brick, slag brick, timber, plasterboard, formations such as shaving board.
Solid or foam stratiform protecting materials can be the polystyrene sheet material of foaming etc.
The following example is for example understood some form of the present invention, but should not regard the restriction to the scope of the invention described in this specification sheets and the claim as.
The preparation of embodiment 1 binding agent
According to following prescription the listed abrasive component of table 1.1 is ground together, in each binder formula, add remaining component then, make binding agent thus.
Table 1.1
Control binder 1 binding agent 1 binding agent 2
Abrasive component
The latex polymer 330.7 330.7 330.7 that negatively charged ion is stable
(Rhoplex
AC-264 latex)
(solid content 60%)
Ammoniacal liquor (28%) 555
Polymethyl acrylic acid 044
Oxazolidinyl ethyl ester (solid content 25%)
Zinc oxide 00 100
Lime carbonate 100 100 0
Anionic dispersing agents 2.5 2.5 2.5
(Tamol
850 dispersion agents)
(total solid content 30%)
Potassium tripolyphosphate 1.5 1.5 1.5
Ethylene glycol 222
Texanol
Coalescing agent 222
(2,2,4-trimethylammonium-3-hydroxyl penta
The base acetic ester)
Defoamer (Nopco
The NXZ defoamer) 444
Clay filler T5 T5 T5
Marble flour 400 400 400
#70 sand 400 400 400
The component of remaining quantity
Water 20 20 20
Natvosol (Natrasol
0.3 0.3 0.3
The HR thickening material)
2 set times of embodiment
Test each binder formula, to determine their how long completely solidified.Each binder formula is cast in scribbles Teflon
ROn glass, with the preparation specimen, its thickness is about 1/32～about 1/16 inch.
Test is 72 of temperature, and relative humidity is carried out for 32.8% time.On each newly formed specimen, put Gardner registering instrument set time.Probe on the instrument once advances by the binding agent surface layer or along surface layer per hour to turn round.The set time of report is with a minute expression, when probe is confirmed as set time along the time that adhesive surface is advanced when not causing any rail trace from the teeth outwards satisfactorily.Be welcome short set time, because this shows that this binding agent has constituted tack and cohesive strength.The results are shown in table 2.1.
Table 2.1
The adhesive cures time (minute)
Reference examples 1 85
1??60
2??35
By the binder formula that the present invention makes, 25 minutes have been shortened its set time (binding agent 1).Contain the binder formula that polyvalent metal makes according to the present invention is optional, shortened totally 50 minutes (binding agent 2-contains zinc oxide) its set time.
The test of embodiment 3 tensile strength
The initial stage tensile cohesive strength of test binder formula demonstrates improved performance to confirm aqueous binders composition of the present invention under all conditions of cure under different conditions of cure.
In a pre-equilibration chamber, adopt certain bi-component epoxy that porous styrofoam disk (thick 1 inch) is glued at (2.25 inches of diameters on the wooden disk; Thick 0.5 inch).In the same way, also plywood glue is adhered to each binder formula of coating one deck on the face veneer of second wooden disk, then polystyrene-the face of first wooden disk is tightly pressed to adhesive layer.Make each sample solidifies again.
Before the test, make all samples equilibrate to test condition.Then sample is placed in the last lower chuck of Instron test machine, then the traction angle perpendicular to tack coat of sample is broken.All samples is all tested with the pinblock speed of 0.5 inch per minute.The tensile strength of report is with pound/square inch expression, and the load (pound) that its numerical value applies when breaking for the Instron machine is with the ratio of test sample surface long-pending (square inch).The results are shown in table 3.1.Tensile strength high when breaking meets the requirements.In addition, the base material type (polystyrene) that breaks is more welcome than the binding agent type that breaks.
Table 3.1
Control binder 1 binding agent 1 binding agent 2
Tensile strength 20.1 25.3 34.4 when breaking
(pound/square inch)
Explain:
Under envrionment conditions, solidified 4 hours
At 75 °F, relative humidity 50% ... warm test down
Adhesive thickness=1/32 inch
Tensile strength 3.4 7.5 13.6 when breaking
(pound/square inch)
Explain:
Under envrionment conditions, solidified 3 hours
At 75 °F, relative humidity 50% ... warm test down
Adhesive thickness=1/8 inch
Tensile strength 16.6 19.0 29.5 when breaking
(pound/square inch)
The broken base material 100% of failure mode binding agent 100% 90% binding agents
Break split/10% base material breaks
Explain:
Under envrionment conditions, solidified 2 hours
At 75 °F, relative humidity 50% ... warm test down
The report value is 5 mean values of measuring
Adhesive thickness=1/16 inch
Tensile strength 21.6 31.4 34.9 when breaking
(pound/square inch)
Failure mode 70% binding agent breaks base material 100% base material 100%
Split/30% base material breaks
Explain:
At 82 °F, relative humidity 94.5% ... warm and moist curing down 5 hours
At 75 °F, relative humidity 50% ... warm test down
The report value is 5 mean values of measuring
Adhesive thickness=1/16 inch
Compare with the binding agent (control binder 1) that does not contain the polymkeric substance of amine, by the binder formula (binding agent 1) that the present invention makes, the tensile strength under two kinds of thickness all increases.If the optional polyvalent metal (binding agent 2 that contains of the binder formula that the present invention makes ... contain zinc oxide), then the tensile strength under two kinds of thickness all improves manyly.
Under thermal condition and very moist condition, by the binder formula (binding agent 1) that the present invention makes, its tensile strength is higher than the binding agent (control binder 1) that does not contain amine-containing polymer.Under wet heat condition and rainy and very moist condition, if the binder formula that the present invention makes contains polyvalent metal (binding agent 2 ... contain zinc oxide), then its tensile strength improves manyly.Under thermal condition, the optional binding agent that contains zinc oxide experiences gratifying 100% base material and breaks by (binding agent 2), and control binder then experiences underproof 100% binding agent and breaks.Under very moist condition of cure, binding agent 1 and binding agent 2 all experience gratifying 100% base material and break.
The test of embodiment 4 shearing resistances
The initial stage shearing resistance of test caking agent formula demonstrates improved performance to confirm aqueous binders composition of the present invention under all conditions of cure under different conditions of cure.
In a pre-equilibration chamber, adopt certain bi-component epoxy that porous rectangle styrofoam sheet (thick 1 inch) is glued on the wood chip (3 inches * 2 inches).By identical method, glued board or cement plate cut into 3 inches * 2 inches small pieces.On glued board or cement plate, apply each binder formula of one deck (thick 1/32-1/16 inch) with a scraper, then the polystyrene face of wood chip is tightly pressed to adhesive layer.Each print is solidified.
Before the test, make all samples equilibrate to test condition.Then sample is placed in the last lower chuck of Tinius Olsen measuring stress instrument, then sample is torn with 180 ° of angles of tack coat.All samples is all tested with the pinblock speed of 0.5 inch per minute.The shearing resistance of report is with the expression of pound/square inch, and its numerical value is that load (pound) that measuring stress instrument applies when tearing amasss the ratio of (square inch) with test sample surface.The results are shown in table 4.1.Shearing resistance high when tearing meets the requirements.In addition, the base material type that breaks is more welcome than the binding agent type that breaks.
Table 4.1
Control binder 1 binding agent 1 binding agent 2
The glued board base material
Shearing resistance 7.5 9.7 11.7 during disconnection
(pound/square inch)
The types of binders of the breaking 100% broken binding agent 90% of binding agent 90% that breaks
Split/base material 10% breaks/base material
10% breaks
Explain: at 75 °F, relative humidity 50% ... warm curing down 3 hours
In 75 ℃ of F, relative humidity 50% ... warm test down
The report value is 2 mean values of measuring
Shearing resistance 9.0 13.1 16.2 during disconnection
(pound/square inch)
The types of binders of breaking 90% broken binding agent 80% broken binding agent 20%
Split/base material 10% breaks and splits/and base material 20% breaks/base material
Break and 80% break
Explain: at 75 °F, relative humidity 50% ... warm curing down 3 hours
In 75 ℃ of F, relative humidity 50% ... warm test down
The report value is 2 mean values of measuring
Compare with the binding agent (control binder 1) that does not contain the polymkeric substance of amine under thermal condition, by the binder formula (binding agent 1) that the present invention makes, the shearing resistance on two types of base materials all increases.Under thermal condition, if the optional polyvalent metal (binding agent 2 that contains of the binder formula that the present invention makes ... contain zinc oxide), then the shearing resistance on two types of base materials all improves manyly.
Claims (18)
1, a kind of aqueous adhesive composition, it comprises:
(a) has a kind of film forming latex polymer of anion characteristic;
(b) by contain a kind of water-soluble or aqueous dispersion polymers that the amine functional group monomer constitutes at least about 20% (weight);
(c) a kind of volatile alkali, its consumption can rise to sufficiently high degree to the PH of composition effectively, and on this occasion, all basically amine functional groups are at the nonionic state.
2, the composition of claim 1 also comprises a kind of water-soluble or water dispersible polyvalent metal.
3, the aqueous adhesive composition of claim 1, wherein said water-soluble or aqueous dispersion polymers is by at least about 50%(weight) monomer that contains amine functional group constitutes.
4, the aqueous adhesive composition of claim 1 wherein constitutes this water-soluble or aqueous dispersion polymers at least about 20%(weight) the amine functional group monomer that contains be N-acrylic acid alkyl-oxazolidines.
5, the aqueous adhesive composition of claim 1, wherein this volatile alkali is an ammonia.
6, the aqueous adhesive composition of claim 2, wherein said water-soluble or water dispersible polyvalent metal is a zinc.
7, a kind of method of improving non-cementaceous water based adhesive tack and cohesive strength, this method comprises:
(a) make a kind of non-cementaceous binding agent that contains following component:
(1) a kind of film forming latex polymer with anion characteristic;
(2) by 20%(weight at least) contain a kind of water-soluble or aqueous dispersion polymers that the amine functional group monomer constitutes;
(3) a kind of volatile alkali, its consumption can rise to sufficiently high degree to the PH of composition effectively, and on this occasion, all basically amine functional groups are at the nonionic state;
(b) non-cementaceous binding agent is coated in the outside surface of buildings or other outdoor structure;
(c) solid or foam stratiform protecting materials are compound on this non-cementaceous binding agent.
8, the method for claim 7, wherein non-cementaceous binding agent also comprise a kind of water-soluble or water dispersible polyvalent metal.
9, the method for claim 7, wherein this water-soluble or aqueous dispersion polymers is by at least about 50%(weight) monomer that contains amine functional group constitutes.
10, the method for claim 7 wherein constitutes this water-soluble or aqueous dispersion polymers at least about 20%(weight) the amine functional group monomer that contains be N-acrylic acid alkyl-oxazolidines.
11, the method for claim 7, wherein this volatile alkali is an ammonia.
12, the method for claim 8, wherein this water-soluble or water dispersible polyvalent metal is a zinc.
13, a species complex, it comprises:
(a) a kind of base material;
(b) a kind of aqueous binding agent, it is made of following component:
(1) a kind of film forming latex polymer with anion characteristic;
(2) by about 20%～about 100%(weight) contain a kind of water-soluble or aqueous dispersion polymers that the amine functional group monomer constitutes;
(3) a kind of volatile alkali, its consumption can rise to sufficiently high degree to the PH of composition effectively, and on this occasion, all basically amine functional groups are at the nonionic state;
(c) be adhered to layer of material on this base material.
14, the complex body of claim 13, wherein aqueous binding agent also comprise a kind of water-soluble or water dispersible polyvalent metal.
15, the complex body of claim 13, wherein this water-soluble or aqueous dispersion polymers is by at least about 50%(weight) monomer that contains amine functional group constitutes.
16, the complex body of claim 13 wherein constitutes this water-soluble or aqueous dispersion polymers at least about 20%(weight) the amine functional group monomer that contains be N-acrylic acid alkyl-oxazolidines.
17, the complex body of claim 13, wherein this volatile alkali is an ammonia.
18, the complex body of claim 14, wherein this water-soluble or water dispersible polyvalent metal is a zinc.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US96548692A | 1992-10-23 | 1992-10-23 | |
| US07/965,486 | 1992-10-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1086241A true CN1086241A (en) | 1994-05-04 |
Family
ID=25510036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93118774A Pending CN1086241A (en) | 1992-10-23 | 1993-10-23 | Quick-set non-cementitious adhesive |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JP3292258B2 (en) |
| KR (1) | KR940009310A (en) |
| CN (1) | CN1086241A (en) |
| BR (1) | BR9304248A (en) |
| CA (1) | CA2108491A1 (en) |
| MX (1) | MX9306398A (en) |
| ZA (1) | ZA937537B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10717879B2 (en) * | 2015-09-30 | 2020-07-21 | Dow Global Technologies Llc | Shelf-stable aqueous composition and process of making the same |
-
1993
- 1993-06-28 JP JP15761893A patent/JP3292258B2/en not_active Expired - Fee Related
- 1993-10-12 ZA ZA937537A patent/ZA937537B/en unknown
- 1993-10-14 MX MX9306398A patent/MX9306398A/en unknown
- 1993-10-15 BR BR9304248A patent/BR9304248A/en not_active Application Discontinuation
- 1993-10-15 CA CA002108491A patent/CA2108491A1/en not_active Abandoned
- 1993-10-21 KR KR1019930021891A patent/KR940009310A/en not_active Application Discontinuation
- 1993-10-23 CN CN93118774A patent/CN1086241A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CA2108491A1 (en) | 1994-04-24 |
| JPH06316691A (en) | 1994-11-15 |
| ZA937537B (en) | 1994-05-16 |
| BR9304248A (en) | 1994-06-14 |
| JP3292258B2 (en) | 2002-06-17 |
| MX9306398A (en) | 1994-04-29 |
| KR940009310A (en) | 1994-05-20 |
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