JPS62270658A - Abrasion resistant polymer composition and coating - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION BACKGROUND OF THE INVENTION The present invention generally relates to wear-resistant polymer and coating compositions;
More particularly, it relates to polymers and coatings that resist wear caused by entrained solids in fluid flow environments.

It is often necessary to move fluids containing entrained solids through conduits such as pipes or tubes. The interior of such conduits often undergoes wear as fluid/solid mixtures move through them. this is,
This is a particular problem in hydroelectric power plants where water containing entrained solids is moved through a suction pipe to rotate impeller blades and generate electricity. Over a period of time, wear from entrained solids can destroy the untreated Q+9191 surface or remove the protective a-covering. In the latter case, the evacuation tube of the conduit must be closed and re-covered.

Polymers and/or materials that resist wear on the inner walls of conduits in fluid flow environments, particularly when the fluid contains entrained solids.
The [E] becomes necessary.

SUMMARY OF THE INVENTION The present invention provides polymer and coating compositions containing approximately 24-48% by weight of the polymer and coating composition.
about 24-48% by weight blocked isocyanate prepolymer, about 4.2-12% by weight rheology additive, about 10-14% by weight curing agent for the epoxides and isocyanates, about 1 We provide wear-resistant polymer compositions and coatings containing ~4% by weight plasticizer and about 0.1-0.6% by weight silane group-containing surface modifier. Optionally, the polymeric compositions and coatings include up to about 2% by weight pigment to aid in visualization to confirm thorough mixing and about 2% by weight fillers or adjuvants to aid in handling. It can contain. Preferably, about 14-2% by weight filler is used.

The polymer or collar is produced by mixing the first and second components of the polymer composition and curing the mixture. The first component is a mixture of about 30-60% by weight liquid epoxy resin, about 30-60% blocked isocyanate prepolymer, and about 5-20% rheology additive. The second component includes a hardening agent of about 1 to 4 weight percent, a plasticizer of about 5 to 20 weight percent, and about 0.5 weight percent of a plasticizer.
It is a mixture of ~3% by weight surface modifier and about 5-20% by weight IAI rheology additive. Four parts by weight of the first component are mixed with one part of the second component, and the resulting mixture is cured to form a polymer.

When this mixture is applied to a surface or substrate and cured, a coating is produced.

In a preferred embodiment, the blended composition includes about 364 weight percent epoxy resin, about 36.4 weight percent blocked isocyanate prepolymer, about 998 weight percent rheology additive, and about 12.84 weight percent A curing agent preferably polyglycol diamine, a plasticizer preferably diptylphthalate of about 2.88% by weight, and a silane group-containing surface modifier of about 36% by weight.

DETAILED DESCRIPTION OF THE INVENTION It is to be understood that the following ingredients in the composition include all equivalents as recognized in the art.

Any suitable liquid epoxy resin may be used, provided that at least 50% by weight, preferably 80% by weight, and most preferably 100% of the liquid epoxy resin used is bisphenol A-shrimp chlorohydrin epoxy resin. do. A preferable resin is 182 to 190
Epoxy equivalent weight of , viscosity of 11,000 to 14,000 (
cp at 25°C) and specific gravity of t16 (25/25°C
) is available. The most preferred bisphenol A-shrimp chlorohydrin resin is a diglycidyl ether of bisphenol A having a theoretical formula (%). "D, E, R" manufactured by Dow Chemical Corporation of Midland, Michigan, USA
, 331'' are particularly preferred.

Up to about 50% by weight of the liquid epoxy resin and preferably about 20% by weight of the bisphenol A-shrimp chlorohydrin resin of the present invention.
Examples of some liquid epoxy resins that can be used in amounts up to 1 are low viscosity epoxy phenolic novolak resins. The preferred resin is 0
．． 54~Q, 58 epoxy value (equivalent/1009), 3
It has a sugar content of 0.000 to so, o o o (cp at 25°C) and a theoretical structural formula. "Epo" with a functionality of 2 to 4 manufactured by Ciba Geigy Corporation
xy Re51n XB 55 S 7'' is particularly preferred.

any suitable block toic anate prepolymer,
In particular, alkylphenol blocked diisocyanates and blocked isocyanate terminated polyether brevolimers can be used. Preferred alkylphenol blocked prepolymers are alkylphenol blocked toluene diisocyanates having ether and blocked urethane groups. This prepolymer is
Experimentally determined equivalents of 860-t000, t at 20°C
Specific gravity of OS and 900±s 00 P at 25°C
It has a viscosity of an. Particularly preferred is "Desmocap'+IA" manufactured by Mobay Chemical Corporation, Bittspurg, Pennsylvania, USA. Another preferred blocked isocyanate has a specific gravity of t04 at 20°C, equivalent weight of 2,470, 24000 to 4 K, 000 c at 25°C.
The alkylphenol-blocked toluene diisocyanate polyether prebolimate has a viscosity of p and 17% of available isocyanate groups. “Desm manufactured by Mobay Chemical Corporation
Particularly preferred is ocap 12''.

For best results, K should be comprised of at least about 80 parts by weight of the blocked toluene diisocyanate prepolymer, preferably 90 parts by weight, and most preferably 100 parts by weight of the alkylphenol blocked toluene diisocyanate brevolimer described above. It is. The remainder of the blocked anate prepolymer may be any blocked anate prepolymer that is compatible with the alkylphenol blocked toluene diisocyanate and does not unblock under the curing conditions.

Any suitable curing agent for epoxides and isocyanates that reacts to cure these components at the same rate under the curing conditions described in and can be used.

Generally, aliphatic and cycloaliphatic amines such as alkylene amines are used, including diamino ethers having terminal primary amino groups. Isophorone diamine, 3-aminomethyl-5,5,5-)limethylcyclohexylamine, 3,31-dimethyl-4,41-diaminodicyclohexylmethane, and polyglycol diamine can be used alone or in combination. The most preferred alkylene amines (referred to herein as polyglycol diamines) have molecules of about 220 t and the formula NH! CH
t CHt CHt O(C)Tt CHs O)t
CHt CHx CHsNH*. "Polygl" manufactured by Union Carbide Corporation located in New York, New York, USA.
Particularly preferred is coldlamne H=2211.

As the rheology additive of the present invention, any additive that improves the flow of the paste or putty-like composition of the present invention and/or provides anti-drip properties to it can be used. Preferably, colloidal silica or hydrophobic fumed silica, especially one surface-modified with polymethylsilyl groups, is used.

Surface modification is achieved by treating the silica with organosilicon to provide surface methyl groups in addition to surface hydroxyl groups. Rheological additives are important in maintaining the shelf life of the paste or putty-like compositions of the present invention and their specific properties. Cab manufactured by Cabot Corporation of Chuscola, Illinois, USA
-0-5ilN70TS" is a particularly preferred rheological additive. Also preferred are organic derivatives of montmorillonite clay, e.g. treated with quaternary ammonium chloride. Most preferred are N.L. Industries Ind. Coholated product “Ben”
tone SD-2” rheology additive.

Any suitable plasticizer can be used in the compositions and coatings of the present invention. Although plasticizers are often thought to impart slip properties to compositions, they actually promote adhesion of the compositions and coatings of the present invention. Some suitable plasticizers include kiphthalates such as alkyl benzyl phthalates, benzyl heptatalates, and dialkyl phthalates. Dibutyl phthalate is preferred.

Any suitable surface modifier containing silane groups,
Any suitable surface modifier capable of reacting with the mineral filler and reactive material of the coating to bond the filler to the polymeric matrix, particularly to the epoxy binder, and to the metal oxide of the substrate to be coated. preferable. Reactive silanes provide stronger compositions and promote adhesion to substrates, especially metals such as aluminum and steel. Suitable surface modifiers that may be used include silanes, particularly organic silane esters known as gamma-aminoalkyltrialkoxysilanes.
“5ilane from Carbide Corporation
γ-aminopropyltriethoxysilane (NHz (CH*)s
S i (OCt Hs )s ).

Epoxysilanes, aminosilanes, or both can be used in combination with liquid epoxy resins, curing agents, or both to provide silane functionality, thereby eliminating the need to use a separate surface modifier reactant. Organic groups (epoxies, amines) react with the organic matrix, and silanols act as fillers and/or
Reacts with metal oxide surfaces. Epoxy and aminosilanes that can be used include γ-glycidoxypropyltrimethoxysilane, β-(44-epoxycyclohexyl)ethyltrimethoxysilane, N-
(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane N
I -β-(aminoethyl)-N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-
Mention may be made of β-(aminoethyl)-γ-aminopropyltrimethoxysilane and analogs and mixtures thereof. When using epoxysilanes and/or aminosilanes, the polymers of the present invention have CL1-α as described here.
An amount is used to provide six silane groups.

Any suitable auxiliary substances, such as fillers, may be used to aid in the handling of the components or compositions of the invention, but they are not necessary for the practicality of the compositions.

Some of the substances include talc, clay, silica, mica, etc. A preferred filler is magnesium silicate, particularly "Nyta 144" manufactured by R.T. Panderbilt Company, Inc., Norwalk, Conn., USA.
0”.

Pigments can be used to facilitate visual confirmation of thorough mixing, but they are not necessary for the practicality of the composition. The polymer compositions and coatings of this invention can be produced using any first pigment in the first component and any second colorant pigment in the second component to be mixed. Some suitable pigments include titanium dioxide, particularly "R-902Titanium Dio" from DuPont, Wilmington, P.A.
xide”, “5unfast Blue”, manufactured by Sun Chemical Corporation, Cincinnati, Ohio, USA, “Irgazin Yellow”, Tetrachlorinintrinon, manufactured by Ciba-Geigy Corporation, “Irgazin Yellow”
w 2GLTE” manufactured as “Pigrnen”
t Yellow 109''. The yellow pigment in one component and the contrast in the other component result in a homogeneous green color indicating thorough mixing.

Although the coating compositions of the present invention can be applied as is to any surface requiring protection against abrasion, they clean such surfaces and remove scale, dirt, flakes, grease, oil, and water. or other foreign substances detrimental to adhesion and cohesion are preferably removed. The surface should then be roughened using any suitable means such as grid blasting, abrasive wheels, files, sandpaper or the like. Generally, the surface is then washed or wiped, preferably with a solvent that leaves no residue, and preferably at least twice, and then thoroughly dried. The surface is then coated with any suitable primer, such as those well known for priming surfaces such as aluminum, steel, concrete, wood, plastic, and the like. Preferred compositions contain an epoxy polyamide as the primer compound, where the epoxy is preferably any of those disclosed herein, especially diglyndyl ether of bisphenol A, and the polyamide has an amine value of 230 to 246. and a reaction product of dimerizing alcohol stain and diethylenetriamine having a viscosity of 20-42 price at 75°C. Particularly preferred epoxy primers are:
“PM-Epoxit Primer” is a product of Balmer International Corporation.
It is.

The polymer composition of the present invention can be deposited on a vertical surface for about 2 hours without dropping.
It can be applied in thicknesses up to 1.5 in. and cured in place. Generally, curing is carried out at ambient temperature and pressure, usually 15-60°C, preferably 20-60°C, most preferably 40°C. Typically pressure is not a consideration and no external pressure is applied. Excellent strength, durability, and adhesion provide high abrasion resistance, flexibility, and elongation, making the coating of the present invention easy to power sand, grind, or remove within 48 hours of application. Can be machined. The coating exhibits virtually no shrinkage during or after curing, repels moisture, and
It has a tensile strength of less than 0.00 psi. The composition also provides excellent abrasion resistance when coated on the inner walls of conduits through which liquids containing entrained solids must pass, and by its paste-like consistency the inner walls of channel pipes. It is particularly useful for patching and filling holes and bits in substrates such as.

In the following description, all parts and percentages are by weight unless otherwise specified, and equivalents may be substituted for each ingredient used.

To produce the preferred polymer compositions and coatings of this invention, two separate components are first prepared.

The first component has an epoxy equivalent weight of 182-190 and 11,0
45.5 parts of bisphenol A-shrimp chlorohydrin liquid epoxy resin with a viscosity of 00~1'4.100, 45.5 parts of alkylphenol blocked toluene diisocyanate with a commercial weight of 860~t000, 0
．． Contains 4 parts titanium dioxide pigment and &6 parts colloidal silica as rheology additive. These materials can be mixed until thoroughly mixed using any currently available automatic mixing and dispensing equipment as well as standard paste mixer equipment such as a double arm mixer, planetary mixer, or dow mixer.

Mixing times can be varied as desired, but about 30 to 45 minutes is usually adequate.

-3 binary components are 64.2 parts of NH, CHtCH, CM,
0(CHg CHg O)t CH, CHg CHt
NH, 14 parts dibutyl phthalate, 18 parts γ-
Aminopropyltriethoxysilane, 56 parts of magnesium silicate, 15.5 parts of colloidal silica as a rheology additive, and 19 parts of "5unfast B"
These materials can be mixed together in any standard mixing equipment such as those described above until thoroughly mixed. About 30 to about 45 minutes is usually adequate.

The two components are brought together just before applying the novel polymer composition of the invention. At this time, 4 parts by weight of the first component are mixed with 1 part by weight of the second component until thoroughly mixed, as indicated by a homogeneous light blue color. Any standard mixing equipment such as those previously described can be used.

The composition is a chickentrope paste with a shelf life of about 40 minutes, during which time it can be applied to the surface to be coated by any suitable means, such as a trowel or spatula. Thicknesses of about 1/16 to about 2 inches are generally suitable. The applied composition cures in about 40 minutes at ambient temperature.

The effectiveness of the coating compositions of the present invention in protecting surfaces from wear by entrained solids in fluid flow environments such as the interior of draft pipes used in hydroelectric power plants can be illustrated by the results of taper wear tests. . Specifically speaking, 1
．． OOO, using C8-17 wheels with @load
An average wear loss of only 1029 per 000 cycles was observed, compared to a typical epoxy proofing which lost as much as 10 times its weight.

As the invention may be embodied in other specific forms without departing from its spirit or essential characteristics, reference should be made to the claims rather than to the foregoing description as indicating the scope of the invention. .

Same as Hiroshi Kazama 1. ·'debt !

Claims (1)

[Scope of Claims] 1. about 24 to 48% by weight liquid epoxy resin;
~48% by weight blocked isocyanate prepolymer and about 10-1% for the epoxide and isocyanate.
4% by weight curing agent, about 4.2-12% by weight rheology additive, about 1-4% by weight plasticizer, and about 0.1-0% by weight plasticizer.
．． A wear-resistant polymer containing 6% by weight of a reaction product with a silane group-containing surface modifier. 2. About 36.4% by weight epoxy resin, about 36.4% by weight blocked isocyanate prepolymer, about 9.9
8% by weight rheology additive, about 12.84% by weight curing agent, about 2.88% by weight plasticizer and about 0.36% by weight.
2. A polymer according to claim 1, which contains a surface modifier. 3. About 24-48% by weight of liquid epoxy resin and about 24% by weight of liquid epoxy resin;
~48% by weight blocked isocyanate prepolymer and about 10-1% for the epoxide and isocyanate.
4% by weight curing agent, about 4.2-12% by weight rheological additive, about 1-4% by weight plasticizer, and about 0.1-0% by weight.
．． Abrasion-resistant coating containing 6% by weight of reaction product with silane and auxiliary substances. 4. About 36.4% by weight epoxy resin, about 36.4% by weight blocked isocyanate prepolymer, about 9.9%
The coating of claim 3 containing 8% by weight rheology additive, about 12.84% by weight polyglycol diamine, about 2.88% by weight dibutyl phthalate and about 0.36% by weight silane. . 5. The epoxy resin is diglycidyl ether of bisphenol A, the blocked isocyanate is alkylphenol blocked toluene diisocyanate,
The curing agent has the formula NH_2CH_2CH_2CH_2O(CH_2CH_
2O)_2CH_2CH_2CH_2NH_2, the rheology additive is colloidal silica, the plasticizer is dibutyl phthalate,
4. A coating according to claim 3, wherein the silane is gamma-aminopropyltriethoxysilane and the auxiliary substance is magnesium silicate. 6. The coating of claim 3 containing up to about 2% by weight of pigment. 7. The coating of claim 3 containing up to about 2% by weight of magnesium silicate. 8. The coating of claim 3 containing about 0.4 to 2% by weight of magnesium silicate. 9. The coating of claim 3, wherein at least about 50% by weight of the liquid epoxy resin is bisphenol A-epichlorohydrin epoxy resin. 10. The coating of claim 3, wherein at least about 80% by weight of the blocked isocyanate prepolymer is an alkylphenol blocked toluene diisocyanate. 11. (a) about 30 to 60% by weight liquid epoxy resin;
about 30-60% by weight of a blocked isocyanate prepolymer and about 4-10% by weight of a rheological additive to form a first portion of the coating; (b) about 50-70% by weight for the epoxide and diamine; curing agent, about 5 to 2
(c) mixing 0% by weight plasticizer, about 0.5-3% by weight silane, and about 5-20% by weight rheology additive to form a second part of the coating; (c) first part 4 of said coating; the second part 1 of said coating in part
(d) applying said composition to a surface; and (e) curing said composition to form a coating. . 12. The first portion is about 45.50% by weight epoxy resin;
about 45.50% by weight blocked isocyanate prepolymer and about 8.60% by weight rheology additive, and the second portion contains about 64.20% by weight curing agent, about 1
12. The method of claim 11, comprising 4.00% by weight plasticizer, about 1.80% by weight silane, and about 15.50% by weight rheology additive. 13. The method of claim 11, wherein each part additionally contains a substance selected from the group consisting of pigments, mineral fillers and mixtures thereof. 14. The method of claim 11, wherein the coating is applied to the surface to a thickness of about 1/6 to 2 inches. 15. The method of claim 11, wherein the composition is cured at ambient temperature. 16. The epoxy resin is a diglycidyl ether of bisphenol A, the blocked isocyanate is an alkylphenol blocked toluene diisocyanate, and the curing agent has the formula NH_2CH_2CH_2CH_2O(CH_2CH_
2O)_2CH_2CH_2CH_2NH_2, the rheology additive is colloidal silica, the plasticizer is dibutyl phthalate,
12. The method of claim 11, wherein the silane is gamma-aminopropyltriethoxysilane and the second portion contains magnesium silicate. 17. The method of claim 16, wherein the first and second portions contain pigments. 18. The method of claim 11, wherein the surface to which the composition is applied is coated with a primer.