CN103709923A - Wear-resistant spraying polyurethane resin composition, and preparation method and construction method thereof - Google Patents
Wear-resistant spraying polyurethane resin composition, and preparation method and construction method thereof Download PDFInfo
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Abstract
The invention discloses a wear-resistant spraying polyurethane resin composition, and a preparation method and construction method thereof. The composition comprises a component A and a component B, wherein the component A comprises the following components in parts by mass: 35-70% of polymer polyalcohol A, 3-9% of plasticizer and 25-60% of isocyanate; the NCO/OH mole ratio is 1.5-5.72; the component B comprises the following components in parts by mass: 13-30% of organic amine curing agent, 0-75% of plasticizer, 0-80% of polymer polyalcohol B and 0.1-1% of catalyst; and the volume ratio of the component A to the component B is 100/50-100/100. The composition is suitable for high-pressure spraying and static mixed spraying, can be sprayed at room temperature or under heating conditions, is not sensitive to humidity, and can not have the phenomenon of foaming or bulging even in an environment with the relative humidity of higher than 70% or on a wet base surface basal plane or under the condition of construction in rainy days, thereby achieving the effect of spraying polyurea. The obtained coating has favorable wear resistance.
Description
Technical field
The present invention relates to spraying polyurethane field, particularly the preparation of wear-resistant polyurethane coating and constructional method.
Background technology
Iron ore is because lean ore is many and association has the comprehensive ore deposit of other components many, the hardness ratio of ore is larger, the magnet drum cylinder skin of magnetic separator is constantly subject to the impact of the granular iron ore below 0～15mm in using, serious wear, so the situation that magnet drum cylinder skin is galled by ore often occurs magnetic separator.Once a cylinder shelling is worn, ore pulp will enter magnet drum be adsorbed on magnetic be surface cause a skin and magnetic be between locking, or ore pulp enters into bearing and causes bearing damage.Magnetic system is the heart of magnetic separator equipment, and when magnetic, system is damaged, and will cause whole magnetic plant paralysis, and it is very important resolving a skin protection.Cylinder skin protective layer is a kind of reinforcing to permanent magnetic cylinder type magnetic separator cylinder, is effective means of extending skin life-span.
In Japanese Patent (the flat 2-258877 of JP), a kind of spray urethane method for producing elastomers is disclosed, be to be obtained by mixing with a kind of resin Composition by polyisocyanates, polytetramethylene ether dibasic alcohol etc., this resin Composition is to be obtained by mixing by polytetramethylene ether dibasic alcohol, elite chainextender, bismuth organic compound catalyzer etc.Gained elastomerics has high-density, high strength and high heat resistance energy.The spray polyurethane elastic body that this patent adopts organic bismuth catalyst to make, only at molding temperature 6.3-27.8 ℃, has examined or check mouldability and the curability of material under relative humidity 30%-68% condition.In fact working-yard relative humidity is usually greater than 68%, and the material of constructing under such environment can foam, and loses mouldability; This patent also must be used high-pressure sprayer.
The polyureas spraying polyurethane coating that Chinese patent CN102108243B is used expensive Amino Terminated polyether(ATPE) to prepare, its wear loss can be low to moderate 0.07cm
3/ 1.61km.
Summary of the invention
For easily foaming, bulge under existing spraying polyurethane resin high humidity environment, the deficiency of wear no resistance, work-ing life is short, first technical problem that the present invention will solve is to provide a kind of wear-resisting spraying polyurethane resin combination, and said composition can be greater than construction under 70% environment and not foam in relative humidity.
Second technical problem that the present invention will solve is to provide a kind of preparation method of said composition.
The 3rd technical problem that the present invention will solve is to provide a kind of constructional method of this resin combination.
Wear-resisting spraying polyurethane resin combination provided by the invention, comprises following composition by mass:
A component: polymer polyatomic alcohol A35%～70%, softening agent 3%～9%, isocyanic ester 25%～60%, NCO/OH mol ratio is 1.5～5.72; NCO%=4.5%～16%.
B component: organic amine curing agent 13%～30%, softening agent 0%～75%, polymer polyatomic alcohol B0%～80%, catalyzer 0.1%～1%.
The volume ratio of A and B is 100/50～100/100.
Described polymer polyatomic alcohol A comprises blend, polytetrahydrofuran diol and the polycaprolactone glycol of polytetrahydrofuran dibasic alcohol, polycaprolactone dibasic alcohol or trivalent alcohol, poly(propylene oxide) dibasic alcohol or trivalent alcohol, polytetrahydrofuran dibasic alcohol and poly(propylene oxide) dibasic alcohol or trivalent alcohol or the blend of trivalent alcohol etc.Wherein, polytetrahydrofuran diol comprises tetrahydrofuran (THF) and 3-methyltetrahydrofuran copolyether dibasic alcohol, tetrahydrofuran (THF) and 3,3-dimethyl trimethylene oxide copolyether dibasic alcohol or tetrahydrofuran (THF) and 3-methyltetrahydrofuran copolyether dibasic alcohol etc.
Described catalyzer comprise rare earth metal complex catalyzer, organic mercury catalyzer or rare earth metal complex catalyzer and organic bismuth catalyst catalyst compounded.The mass ratio of rare earth metal complex catalyzer and organic bismuth catalyst is advisable to be not less than 2/1.Unfavorable to environmental protection because of organic mercury catalyzer, should adopt environment amenable catalyzer as far as possible.Organic bismuth catalyst is as three neodecanoic acid bismuths etc.; Rare earth metal complex catalyzer, as the CUCAT catalyst series of Guangzhou You Run synthetic materials company limited production.
Described polymer polyatomic alcohol B comprises under polyether glycol and normal temperature being liquid polyester polyol.Polyether glycol can be polytetrahydrofuran diol, the equal polyethers of propylene oxide or with oxyethane copolyether etc.Under normal temperature, be liquid polyesters polyvalent alcohol, such as hexanodioic acid neopentyl glycol butanediol ester, adipate glycol glycol ether ester, diethylene glycol adipate, polycaprolactone polyol etc.
For further improving wear resistance, reducing costs, improve performance and improve processing performance, in B component, also can add wear resistant filler, as one or more the mixture in silicon carbide, hollow glass micropearl, ceramic microsphere, aluminium sesquioxide, titanium dioxide, molybdenumdisulphide, graphite etc.Consumption is 0%～3.5% of B constituent mass, and preferably addition is 2%～2.5%.
Described isocyanic ester is as one or more the mixture in aromatic diisocyanate, aromatic polyisocyanate or modified aromatic family isocyanic ester etc.As tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI); Modified isocyanate is as liquefied mdi of Carbodiimide-Modified etc.The functionality of isocyanic ester is generally 2.0～2.3.
Described softening agent is as the ester of aromatic series or aliphatic dibasic alcohol and lipid acid generation, comprise dibutyl phthalate, dioctyl phthalate (DOP), diisononyl phthalate, dioctyl terephthalate, dioctyl succinate, Octyl adipate, dioctyl sebacate, dipropyl carbonate or 2,2,4-trimethylammonium-1,3-pentanediol diisobutyrate etc.
Described organic amine curing agent is as 3,5-diethyl toluene diamine (DETDA), 3,5-dimethythiotoluene diamine (DMTDA), 2,4-diamino-3,5-dimethyl sulphur-based chlorobenzene (TX-2), 2,4-diamino-3-methylthio group-5-propyltoluene (TX-3), N, one or more in N '-dialkyl methyl diamines etc.
In the reaction of preparation A component, add low molecular weight diol, to improve coating initial strength.As 1,3 butylene glycol, dipropylene glycol or glycol ether etc., be generally no more than 2.5% of A constituent mass.
In above-mentioned polyurethane resin composition B component, also can add appropriate rheology control agent as aerosil, organic bentonite or polymeric amide etc.Also can add defoamer, as the German BYK product BYK-555 of chemical company, silicane defoamer etc., preferably add-on is 0.1%～0.5% of B composition weight.
Present composition preparation method comprises following steps:
(1) A component preparation: the isocyanic ester of metering is added in reactor, add the polymer polyatomic alcohol A and the softening agent that have dewatered, react 1.5-2h at 75～80 ℃, sampling analysis isocyanate group content reaches after required value, and cooling discharge seals standby.
(2) B component preparation: organic amine solidifying agent, softening agent, polymer polyatomic alcohol B, catalyzer, selectivity added ingredients by metering, at 50 ± 2 ℃, mix 1h, discharging sealing is preserved.
Spraying polyurethane resin combination of the present invention had both been suitable for high pressure painting and had also been suitable for static mixing spraying, can be at room temperature or the situation of heating carry out spraying operation, static mixing spraying coating process comprises the following steps:
(1) spray finishing material is packed in double-cylinder type packing;
(2) load onto flow restrictor, mixing tank/nozzle;
(3) utilize the coupling mechanism that can connect fast that spray gun is connected with pressurized air, after described A, two components of B are measured, pressurize, are heated up in the static mixing type two component spray equipment of 1:1～2:1 fixed volume ratio, by spray gun, be sprayed onto on ground, solidify to obtain spray polyurethane elastic body material.The air pressure of using is 5～9Bar, and best operation pressure is 6～7Bar.
Polyurethane composition of the present invention has following advantages:
1. pair humidity is insensitive, though relative humidity be greater than under 70% environment or on moist basal plane even construction on rainy day also without foaming, bulge phenomenon, reach the effect of spray polyurea;
2. wear resistance is good;
3. spraying polyurethane resin combination of the present invention had both been suitable for high pressure painting and had also been suitable for static mixing spraying, and as adopted Spray glue rifle, the technique of static mixing is constructed.
The remarkable advantage of polyureas spraying polyurethane resin is insensitive to the humidity of working-yard, but conventionally will use the Amino Terminated polyether(ATPE) of price.The present invention is use side amino-polyether not, by using rare earth metal complex catalyzer or rare earth metal complex catalyzer and organic bismuth catalyst composite, make non-polyureas spraying polyurethane resin, have with polyureas spraying polyurethane resin equally to the insensitive advantage of working-yard humidity.Gained elastomerics can be used for the wear-resisting application places of having relatively high expectations of profiled material such as the drums for magnetic separation machine coating, spiral chute coating, floatation equipment lining in mine.Performance can meet the requirement of these application, has advantages of that construction technology is good, it is low to wear away.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Preparation technology in specific embodiment is as follows:
(1) A component preparation:
By raw material shown in table 1, add in reactor, in nitrogen atmosphere, in 75～80 ℃ of reaction 2h, obtain A component.
(2) B component preparation:
By raw material shown in table 2, add in reactor, mix, obtain B component.
Embodiment 1-5 and comparative example raw materials used in Table 1, table 2.Wherein main raw material code name is described as follows:
MDI: diphenylmethanediisocyanate;
MDI-50: diphenylmethanediisocyanate (4,4 '-, 2,4 ' isomer respectively account for 50%)
TDI: tolylene diisocyanate;
PTMEG-1000: polytetramethylene ether diol, relative molecular mass 1000 ± 50;
PTMEG-650: polytetramethylene ether diol, relative molecular mass 650 ± 25;
GE-210: poly(propylene oxide) dibasic alcohol, OH=107-117mgKOH/g;
EP-551C, poly(propylene oxide) trivalent alcohol OH=54-58 mgKOH/g, the large Chemical Group in east, Shandong;
GE-220, poly(propylene oxide) dibasic alcohol OH=54.5-57.5 mgKOH/g;
PCL205: the polycaprolactone glycol of relative molecular mass 530, Japanese Daisel chemical industry Co., Ltd;
PDN: hexanodioic acid neopentyl glycol butanediol ester, OH=53-59mgKOH/g;
TXIB:2,2,4-trimethylammonium-1,3-pentanediol diisobutyrate;
DETDA:3,5-diethyl toluene diamine;
Wandalink6200:N, N '-dialkyl methyl diamines, Yantai Wanhua Polyurethane Co., Ltd;
CUCAT: rare earth metal complex catalyzer, Guangzhou You Run synthetic materials company limited;
BYK555: defoamer Germany BYK chemical company;
Hollow glass micropearl: Minnesota Mining and Manufacturing Company;
Aerosil: German Degussa company;
First, the front all functions that check spray gun of double-cylinder type wrapping material are installed.The coupling mechanism that utilization can connect fast couples together spray gun and compressed air line.A component and B component take volume ratio 1:1～1:2 in air pressure under 6～7Bar, adopt Spray double-cylinder type packing to construct.Before operation, guarantee anhydrous in pressurized air and oily substance.
Feed liquid obtains by spraying the test piece that thickness is about 2mm, and test piece is cultivated 7 days in 23 ℃ of thermostatic chambers, and by its physicals of following standard test, test result is in Table 3.
Table 1A component feeding quantity (g)
Table 2B component feeding quantity (g)
The salient features of table 3 coating
As can be seen from Table 3, the polyurethane material making by the inventive method has good comprehensive mechanical property, especially wear away low, at high humidity environment, construct without foamed phenomenon, film surface compact is smooth, can meet the wear-resisting application requiring of having relatively high expectations of profiled material such as drums for magnetic separation machine coating, spiral chute coating, floatation equipment lining.
Claims (10)
1. a wear-resisting spraying polyurethane resin combination, comprises following composition by mass:
A component: polymer polyatomic alcohol A35%～70%, softening agent 3%～9%, isocyanic ester 25%～60%, NCO/OH mol ratio is 1.5～5.72; NCO%=4.5%～16%;
B component: organic amine curing agent 13%～30%, softening agent 0%～75%, polymer polyatomic alcohol B0%～80%, catalyzer 0.1%～0.5%;
The volume ratio of A and B is 100/50～100/100;
Described polymer polyatomic alcohol A comprises blend, polytetrahydrofuran diol and the polycaprolactone glycol of polytetrahydrofuran dibasic alcohol, polycaprolactone dibasic alcohol or trivalent alcohol, poly(propylene oxide) dibasic alcohol or trivalent alcohol, polytetrahydrofuran dibasic alcohol and poly(propylene oxide) dibasic alcohol or trivalent alcohol or the blend of trivalent alcohol, wherein, polytetrahydrofuran diol comprises tetrahydrofuran (THF) and 3-methyltetrahydrofuran copolyether dibasic alcohol, tetrahydrofuran (THF) and 3,3-dimethyl trimethylene oxide copolyether dibasic alcohol or tetrahydrofuran (THF) and 3-methyltetrahydrofuran copolyether dibasic alcohol;
Polymer polyatomic alcohol B comprises under polyether glycol and normal temperature being liquid polyester polyol;
Described catalyzer comprise rare earth metal complex catalyzer, organic mercury catalyzer or rare earth metal complex catalyzer and organic bismuth catalyst catalyst compounded.
2. according to wear-resisting spraying polyurethane resin combination claimed in claim 1, it is characterized in that in polymer polyatomic alcohol B polyether glycol refer to polytetrahydrofuran diol, the equal polyethers of propylene oxide or with oxyethane copolyether; Liquid polyester polyol refers to hexanodioic acid neopentyl glycol butanediol ester, adipate glycol glycol ether ester, diethylene glycol adipate or polycaprolactone polyol.
3. according to wear-resisting spraying polyurethane resin combination claimed in claim 1, it is characterized in that the mass ratio of rare earth metal complex catalyzer and organic bismuth catalyst is not less than 2/1, organic bismuth catalyst refers to three neodecanoic acid bismuths.
4. according to the wear-resisting spraying polyurethane resin combination one of claim 1-3 Suo Shu, it is characterized in that isocyanic ester refers to one or more the mixture in aromatic diisocyanate, aromatic polyisocyanate or modified aromatic family isocyanic ester.
5. according to wear-resisting spraying polyurethane resin combination claimed in claim 4, it is characterized in that isocyanic ester refers to tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI); The liquefied mdi of modified isocyanate Carbodiimide-Modified, the functionality of isocyanic ester is 2.0～2.3.
6. according to the wear-resisting spraying polyurethane resin combination one of claim 1-3 Suo Shu, it is characterized in that described softening agent refers to dibutyl phthalate, dioctyl phthalate (DOP), diisononyl phthalate, dioctyl terephthalate, dioctyl succinate, Octyl adipate, dioctyl sebacate, dipropyl carbonate or 2,2,4-trimethylammonium-1,3-pentanediol diisobutyrate.
7. according to the wear-resisting spraying polyurethane resin combination one of claim 1-3 Suo Shu, it is characterized in that described organic amine curing agent refers to 3,5-diethyl toluene diamine (DETDA), 3,5-dimethythiotoluene diamine (DMTDA), 2,4-diamino-3,5-dimethyl sulphur-based chlorobenzene (TX-2), 2,4-diamino-3-methylthio group-5-propyltoluene (TX-3), N, one or more in N '-dialkyl methyl diamines.
8. according to the wear-resisting spraying polyurethane resin combination one of claim 1-3 Suo Shu, it is characterized in that can also adding low molecular weight diol in the reaction of preparation A component, be no more than 2.5% of A constituent mass;
In B component, also can add appropriate rheology control agent, also can add defoamer, add-on is 0.1%～0.5% of B constituent mass.
9. a method of preparing the described wear-resisting spraying polyurethane resin combination of one of claim 1-8, comprises following steps:
(1) A component preparation: the isocyanic ester of metering is added in reactor, add the polymer polyatomic alcohol A and the softening agent that have dewatered, react 1.5-2h at 75～80 ℃, sampling analysis isocyanate group content reaches after required value, and cooling discharge seals standby;
(2) B component preparation: organic amine solidifying agent, softening agent, polymer polyatomic alcohol B, catalyzer by metering, at 50 ± 2 ℃, mix 1h, discharging sealing is preserved.
10. the described wear-resisting spraying polyurethane resin combination static mixing spraying coating process of one of claim 1-8, comprises the following steps:
(1) spray finishing material is packed in double-cylinder type packing;
(2) load onto flow restrictor, mixing tank/nozzle;
(3) utilize the coupling mechanism that can connect fast that spray gun is connected with pressurized air, after described A, two components of B are measured, pressurize, are heated up in the static mixing type two component spray equipment of 1:1～2:1 fixed volume ratio, by spray gun, be sprayed onto on ground, solidify to obtain spray polyurethane elastic body material, the air pressure of use is 5～9Bar.
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| CN108404196A (en) * | 2018-03-23 | 2018-08-17 | 安徽三山新材料科技有限公司 | A kind of bandage spraying slurry |
| CN109535990A (en) * | 2018-11-26 | 2019-03-29 | 新疆天地金阳环保新材料有限公司 | Two-component silicon PU elastic layer and preparation method thereof and sports ground silicon PU material and preparation method thereof |
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| CN109575211A (en) * | 2018-11-23 | 2019-04-05 | 广州优润合成材料有限公司 | Oligomeric coordination heterozygosis organo-metallic catalyst and the preparation method and application thereof |
| CN109535990A (en) * | 2018-11-26 | 2019-03-29 | 新疆天地金阳环保新材料有限公司 | Two-component silicon PU elastic layer and preparation method thereof and sports ground silicon PU material and preparation method thereof |
| CN110922884A (en) * | 2019-12-12 | 2020-03-27 | 山东一诺威聚氨酯股份有限公司 | Polyurethane type spraying elastomer and preparation method thereof |
| CN110845685A (en) * | 2019-12-12 | 2020-02-28 | 中国科学院长春应用化学研究所 | Polyaspartic acid ester and polyurea-based repairing material for repairing polyurethane foam of automobile instrument panel, and preparation method and repairing method thereof |
| CN110845685B (en) * | 2019-12-12 | 2021-11-09 | 中国科学院长春应用化学研究所 | Polyaspartic acid ester and polyurea-based repairing material for repairing polyurethane foam of automobile instrument panel, and preparation method and repairing method thereof |
| CN110977756A (en) * | 2019-12-27 | 2020-04-10 | 万华化学集团股份有限公司 | Polishing layer of chemical mechanical polishing pad and application thereof |
| CN110977756B (en) * | 2019-12-27 | 2021-09-07 | 万华化学集团电子材料有限公司 | Polishing layer of chemical mechanical polishing pad and application thereof |
| CN111675958A (en) * | 2020-07-08 | 2020-09-18 | 王振海 | Protective coating material for ships, naval vessels and offshore drilling platforms and preparation method |
| CN116694216A (en) * | 2023-06-29 | 2023-09-05 | 海洋化工研究院有限公司 | Room-temperature-cured two-component high-strength high-elasticity high-wear-resistance polyurethane resin and preparation method thereof |
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