CN1730551A - Manufacturing method and uses of modified unsaturated polyester resin for composite sculpture - Google Patents
Manufacturing method and uses of modified unsaturated polyester resin for composite sculpture Download PDFInfo
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- CN1730551A CN1730551A CN 200510085013 CN200510085013A CN1730551A CN 1730551 A CN1730551 A CN 1730551A CN 200510085013 CN200510085013 CN 200510085013 CN 200510085013 A CN200510085013 A CN 200510085013A CN 1730551 A CN1730551 A CN 1730551A
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- Prior art keywords
- unsaturated polyester
- polyester resin
- coupling agent
- acid ester
- phosphoric acid
- Prior art date
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Links
- 229920006337 unsaturated polyester resin Polymers 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 24
- -1 unsaturated phosphate ester Chemical class 0.000 claims abstract description 24
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 18
- 239000011147 inorganic material Substances 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 17
- 150000003009 phosphonic acids Chemical class 0.000 claims abstract description 16
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007822 coupling agent Substances 0.000 claims abstract description 13
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 230000003712 anti-aging effect Effects 0.000 claims abstract description 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000002148 esters Chemical class 0.000 claims abstract description 4
- 229920000728 polyester Polymers 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 23
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 21
- 239000000945 filler Substances 0.000 claims description 20
- 229920006305 unsaturated polyester Polymers 0.000 claims description 14
- 229920005989 resin Polymers 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910000077 silane Inorganic materials 0.000 claims description 10
- 239000007921 spray Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 239000005995 Aluminium silicate Substances 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 6
- 235000012211 aluminium silicate Nutrition 0.000 claims description 6
- PZZYQPZGQPZBDN-UHFFFAOYSA-N aluminium silicate Chemical compound O=[Al]O[Si](=O)O[Al]=O PZZYQPZGQPZBDN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 claims description 6
- 239000011159 matrix material Substances 0.000 claims description 6
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- SEILKFZTLVMHRR-UHFFFAOYSA-N 2-phosphonooxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOP(O)(O)=O SEILKFZTLVMHRR-UHFFFAOYSA-N 0.000 claims description 4
- CIIWMXSMCCRQEQ-UHFFFAOYSA-N 3-phosphonooxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCOP(O)(O)=O CIIWMXSMCCRQEQ-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007769 metal material Substances 0.000 claims description 4
- 239000010445 mica Substances 0.000 claims description 4
- 229910052618 mica group Inorganic materials 0.000 claims description 4
- YFLAJEAQOBRXIK-UHFFFAOYSA-N 2-prop-2-enoyloxyethylphosphonic acid Chemical compound OP(O)(=O)CCOC(=O)C=C YFLAJEAQOBRXIK-UHFFFAOYSA-N 0.000 claims description 3
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 3
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 3
- 239000011256 inorganic filler Substances 0.000 claims description 3
- XWCIXXXLOAAWPU-UHFFFAOYSA-N prop-1-enylphosphonic acid Chemical class CC=CP(O)(O)=O XWCIXXXLOAAWPU-UHFFFAOYSA-N 0.000 claims description 3
- UDXXYUDJOHIIDZ-UHFFFAOYSA-N 2-phosphonooxyethyl prop-2-enoate Chemical compound OP(O)(=O)OCCOC(=O)C=C UDXXYUDJOHIIDZ-UHFFFAOYSA-N 0.000 claims description 2
- DOYKFSOCSXVQAN-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CCO[Si](C)(OCC)CCCOC(=O)C(C)=C DOYKFSOCSXVQAN-UHFFFAOYSA-N 0.000 claims description 2
- OFTFNIRYBQZEFP-UHFFFAOYSA-N [hydroxy(propoxy)phosphoryl] prop-2-eneperoxoate Chemical compound CCCOP(O)(=O)OOC(=O)C=C OFTFNIRYBQZEFP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- SXPLZNMUBFBFIA-UHFFFAOYSA-N butyl(trimethoxy)silane Chemical compound CCCC[Si](OC)(OC)OC SXPLZNMUBFBFIA-UHFFFAOYSA-N 0.000 claims description 2
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- ZTWTYVWXUKTLCP-UHFFFAOYSA-L ethenyl-dioxido-oxo-$l^{5}-phosphane Chemical compound [O-]P([O-])(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-L 0.000 claims description 2
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 235000003642 hunger Nutrition 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 claims description 2
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 229960001866 silicon dioxide Drugs 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 238000009472 formulation Methods 0.000 abstract description 3
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- 239000000805 composite resin Substances 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000013461 design Methods 0.000 description 4
- 230000001066 destructive effect Effects 0.000 description 4
- 230000000007 visual effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 2
- FUPMSLTYEIZSLZ-UHFFFAOYSA-N cobalt;naphthalene-1-carboxylic acid Chemical compound [Co].C1=CC=C2C(C(=O)O)=CC=CC2=C1 FUPMSLTYEIZSLZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011152 fibreglass Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000011863 silicon-based powder Substances 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention relates to a manufacturing method and uses of modified unsaturated polyester resin for composite sculpture, which comprises, under the condition of continuous stirring, charging unsaturated phosphoric ester coupling agent or unsaturated phosphonic acid coupling agent and silicane coupling agent simultaneously into unsaturated polyester resin formulation for resin composite sculpture, then charging anti-aging agent and using inorganic material or stuffing material, finally agitating to obtain the modified unsaturated polyester resin, the unsaturated phosphate ester or phosphonic acids coupling agent are monoester or double ester of phosphate ester, or their mixture or phosphonic acid coupling agent.
Description
Technical field
The present invention relates to the manufacture method and the application thereof of the modified unsaturated polyester resin that composite sculpture uses, or relate to the manufacture method of the manufacture method of the modified unsaturated polyester resin that a kind of metal-polyester composite sculpture uses or the high strength modified unsaturated polyester resin that the metal-polyester composite sculpture is used (or being called for short unsaturated polyester), specially referring to and being applied to matallic surface layer is copper, the manufacture method of the high strength remodeling unsaturated polyester resin material (or being called for short unsaturated polyester resin) of stainless metal-polyester composite sculpture goods and other application of this modified unsaturated polyester resin.
Background technology
It is very general that present application unsaturated polyester resin is made sculpture, but great majority adopt simple formulation, and composition is simple, goods are easy to generate cracking, filling settlement and skewness causes focal point of stress, thereby influence product strength, cause product deformation, not attractive in appearance.
Metallic substance has special physico-chemical property, valuable and wear-resisting, for reducing cost, improves product properties, and polyester material is used as the metal carving internal layer, and like this, valuable metal usage quantity can be reduced to original below 1/20.And metal-polyester composite sculpture goods have the artistic effect of metal-like, physics and chemistry burn into that again can anti-natural climate increases the service life in the open, yet, as everyone knows, metal, polyester material linear expansivity differ bigger, and the interface is inconsistent between the two, such interface, and bonding force is less than 6.5MPa usually.
For addressing these problems, people join silane coupling agent in the polyester formulation to improve dispersiveness and the bonding force of inorganic fillers in polyester.But such prescription is very little to the metallic substance effect.
Organophosphate also can be promoted dispersion and the combination of filler in polyester, and the chain alkyl of these compounds combines with polyester layer by solvability, but this bonding force does not reach satisfied result of use yet.
A kind of unsaturated chromic compound often is used in the glass reinforced plastic process industry, and the methacrylic acid chromic compound of this being called as " fertile blue " can improve the intensity of glass reinforced plastic greatly, and result of use is better.But " fertile blue " is a kind of have very dark color and easily resolving compounds, to the goods and the demanding occasion and inapplicable of light color.
Summary of the invention
Technical problem to be solved by this invention is the shortcoming that overcomes prior art, a kind of bonding force that can improve between inorganic materials and the polyester material is provided, the reinforcing filler dispersiveness, make two kinds of materials in the matrix material have the identical or close coefficient of expansion, weather resistance and water tolerance, and can improve product strength, the manufacture method that keeps the high strength modified unsaturated polyester resin that the metal-polyester composite sculpture of good artistic design uses, and other application of the modified unsaturated polyester resin made of this method.
The inventor is through a large amount of practical studies, and discovery cooperates with unsaturated phosphate coupling agent and silane coupling agent or is used in combination and can overcomes the above problems very satisfactorily with cheap cost.Add such composite coupler, not only can improve the bonding force between inorganic materials and the resin material very effectively, promote fillers dispersed, reduce sedimentation, can give the suitable coefficient of expansion of matrix material with formula rate or make the above-mentioned two kinds of materials in the matrix material have the identical or close coefficient of expansion by the kind of selecting following appropriate filler for use simultaneously, weather resistance and water tolerance, thus product strength improved effectively, keep good artistic design.
The manufacture method of the high strength modified unsaturated polyester resin that a kind of metal-polyester composite sculpture of the present invention is used is achieved by following technical proposals:
The manufacture method of the high strength modified unsaturated polyester resin that a kind of metal-polyester composite sculpture is used, following steps are arranged, it is characterized in that: continuing under the stirring condition earlier, in the resin compounded sculpture is filled a prescription with unsaturated polyester resin, add unsaturated phosphate coupling agent and silane coupling agent simultaneously, or add unsaturated phosphonic acid based coupling agent and silane coupling agent simultaneously; Add anti-aging agent again, then according to metal level metal types difference, select packing variety and ratio, so that the resin that has filler to fill is identical or close with the coefficient of expansion of metal level, thereby raising product strength, or by using the inorganic materials or the filler of following consumption, the coefficient of expansion that makes matrix material is identical with the coefficient of expansion of metallic substance or be close, continue to stir, obtain above-mentioned modified unsaturated polyester resin, standby, monoesters that above-mentioned unsaturated phosphate coupling agent is unsaturated phosphoric acid ester or dibasic acid esters or its mixture, above-mentioned phosphoric acid ester or the phosphonic acids usage quantity in unsaturated polyester resin are to use 0.01-10 weight % phosphoric acid ester or phosphonic acids in total unsaturated polyester resin weight; Above-mentioned inorganic materials or filler are selected from silicon-dioxide, lime carbonate, talcum powder, mica powder, pure aluminium silicate, aluminum oxide powder, stone material, one or both in glass fibre or other inorganic materials or two or more mixtures, or be selected from copper powder, aluminium powder, one or both of iron powder or other metal powder or two or more mixtures, the usage quantity of above-mentioned filler in resin is to use the above-mentioned filler of 20-35 weight % in total unsaturated polyester resin weight.
The manufacture method of the high strength modified unsaturated polyester resin that metal-polyester composite sculpture is as previously discussed used, it is characterized in that: said inorganic materials is a metal level, is copper, iron, the spray to cast layer of stainless steel or other metal or alloy, forge make the layer or electroformed layer in a kind of.
The manufacture method of the high strength modified unsaturated polyester resin that metal-polyester composite sculpture is as previously discussed used, it is characterized in that: described unsaturated phosphoric acid ester is the phosphoric acid ester that contains unsaturated link(age): acryloxy ethyl phosphonic acid ester, the methacryloxyethyl phosphoric acid ester, the acryloxy propyl phosphate, the methacryloxypropyl phosphoric acid ester; Two (acryloxy ethyl) phosphoric acid ester, two (methacryloxyethyl) phosphoric acid ester, two (acryloxy propyl group) phosphoric acid ester, one or both in two (methacryloxypropyl) phosphoric acid ester or two or more mixtures; Described insatiable hunger phosphonic acid based is the phosphonic acid based that contains unsaturated link(age): vinyl phosphonate, propenyl phosphonic acids, one or both in the isopropylene phosphonic acid or two or more mixtures.
The manufacture method of the high strength modified unsaturated polyester resin that metal-polyester composite sculpture is as previously discussed used is characterized in that: above-mentioned phosphoric acid ester or the phosphonic acids usage quantity in unsaturated polyester is for using above-mentioned phosphoric acid ester or the phosphonic acids of 0.01-5 weight % in total unsaturated polyester resin weight.
The manufacture method of the high strength modified unsaturated polyester resin that metal-polyester composite sculpture is as previously discussed used is characterized in that: above-mentioned phosphoric acid ester or the phosphonic acids usage quantity in unsaturated polyester resin is for using above-mentioned phosphoric acid ester or the phosphonic acids of 0.1-3 weight % in total unsaturated polyester resin weight.
The manufacture method of the high strength modified unsaturated polyester resin that metal-polyester composite sculpture is as previously discussed used, it is characterized in that: above-mentioned silane coupling agent is variously can strengthen organism and inorganics bonded silicane material: vinyltrimethoxy silane, vinyltriethoxysilane or other vinyl alkoxy silane; Methyltrimethoxy silane, ethyl trimethoxy silane, butyl trimethoxy silane or other alkyl methoxy silane; γ-An Bingjisanjiayangjiguiwan, γ-An Bingjisanyiyangjiguiwan or other amino-contained silane; γ-acryloxy propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, γ-acryloxy propyl group methyl dimethoxysilane, γ-acryloxy propyl group methyldiethoxysilane, γ-methacryloxypropyl methyldiethoxysilane or other γ-acryloxy propyl trialkoxy silane or γ-methacryloxypropyl trialkoxy silane or γ-acryloxy propyl group methyl dialkoxy silicane or γ-methacryloxypropyl methyl dialkoxy silicane; γ-Qiu Jibingjisanjiayangjiguiwan, γ-sulfydryl propyl-triethoxysilicane, γ-sulfydryl propyl group methyl dimethoxysilane, in γ-sulfydryl propyl group methyl dimethoxysilane or other γ-sulfydryl propyl group methyl methoxy base silane or γ-Qiu Jibingjisanjiayangjiguiwan or other silane coupling agent one or both or two or more mixtures, the usage quantity of above-mentioned silane coupling agent in unsaturated polyester resin are the above-mentioned silane coupling agent that uses 0.1-15 weight % in total unsaturated polyester material weight.
The manufacture method of the high strength modified unsaturated polyester resin that metal-polyester composite sculpture is as previously discussed used is characterized in that: the usage quantity of above-mentioned silane coupling agent in unsaturated polyester resin is for using the above-mentioned silane coupling agent of 1-10 weight % in total unsaturated polyester weight.
The manufacture method of the high strength modified unsaturated polyester resin that metal-polyester composite sculpture is as previously discussed used is characterized in that: the usage quantity of above-mentioned silane coupling agent in unsaturated polyester resin is to use the above-mentioned silane coupling agent of 1-5 weight % in total unsaturated polyester material weight.
The modified unsaturated polyester resin that the manufacture method of the high strength modified unsaturated polyester resin of using as above any described metal-polyester composite sculpture is made, in bonding inorganic materials and inorganic materials, or the application in inorganic materials and the polyester.
An important feature of the present invention is different kind and the types of selecting suitable unsaturated polyester according to the sculpture type of manufacturing and requirement: above-mentioned unsaturated polyester, to common sculpture goods, often selecting model cheaply for use is that 191 unsaturated polyester resin is made base resin, occasion to the specific demands such as composite sculpture goods of putting in the fish jar then adopts special S-808 type water tolerance unsaturated polyester resin type;
Another important feature of the present invention is a filler of selecting the unsaturated polyester of concrete kind and formula rate to use according to employed occasion difference:
Because the common thermal expansivity of unsaturated polyester is greater than the expansible coefficient of metal, both excessive coefficient of expansion gaps often make goods cracking occur when being subjected to violent temperature variation, defectives such as flake, and in resin, insert the less filler of the coefficient of expansion, can make the coefficient of expansion and the metal of compound resin very approaching, thereby can prevent the generation of this type of situation, accurate sculpture goods at hot spray to cast stainless steel surface, because the stainless coefficient of expansion is 11.7, and the 191 unsaturated polyester resin coefficients of expansion are bordering on 90-100, for making its thermal expansivity approaching, avoid the product defect that causes because of expanding with heat and contract with cold, select for use the thermal expansivity of 20 weight % to be approximately the mica mixed fillers that 6 pure aluminium silicate filler and the coefficient of expansion are 12 10 weight %, the compound resin layer coefficient of expansion that test contains above filler is about 12, very little with stainless coefficient of expansion difference, therefore can improve the thermostability of goods effectively;
Another important feature of the present invention is the manufacturing requirement at different resin compounded sculpture goods, select suitable unsaturated polyester, make the metal composite sculpture goods of surperficial cast copper, consider product strength and manufacturing cost, can adopt 191 type unsaturated polyester resins, continue to stir and add unsaturated phosphate coupling agent down successively, silicone couplet, anti-aging agent etc., different according to required coefficient of expansion different choice again filler type and ratio, and for example: to the goods of surperficial Spraying-casting copper, the coefficient of expansion that adds 30 weight % is 5.2 pure aluminium silicate filler, continue to stir, standby.The unsaturated polyester resin compositions that makes thus can suitably be deposited and can filling settlement not occur and influence use.When treating to use, mix with promotor, solidifying agent etc. again, pour into a mould under the room temperature, through 4-8 hour curing molding.
The manufacture method of the modified unsaturated polyester resin that metal-polyester composite sculpture of the present invention is used has following beneficial effect compared with prior art:
The present invention cooperates unsaturated phosphoric acid ester and silane coupling agent or is used in combination and can solves the problems of the prior art very satisfactorily with cheap cost:
1) at first can improve bonding force between inorganic materials and the material in polyester resin very effectively, promote fillers dispersed, homogeneity, minimizing so that avoid sedimentation;
2) can give matrix material the suitable coefficient of expansion by kind and the formula rate of selecting above-described filler for use, weather resistance and water tolerance, thereby improve product strength effectively, keep good artistic design, be applicable to and make sculpture, building decoration ornament etc., its matallic surface layer is copper, stainless steel etc.
Embodiment
Embodiment 1
Make high temperature resistant silicon glued membrane tool according to a conventional method, spray copper powder, then use flame line spray to cast method spray to cast bronze layer, coat the polyester resin layer that following each composition mixes or combination is made again in parts by weight:
100 parts of unsaturated polyester resins
20 parts of pure aluminium silicate
10 parts on mica
2 parts of propenyl phosphonic acids
5 parts of γ-methacryloxypropyl trimethoxy silane
Solidifying agent is an amount of
Promotor is an amount of
Anti-aging agent is an amount of,
Be added to certain required thickness gradually, cure and demold.Measure its metal level/non-metallic layer bond strength＞12MPa, the destructive test polyester layer destroys prior to joint.Measure metal level linear expansivity and polyester layer linear expansivity difference less than 1.7; The sculpture goods were placed 6 days at-18 ℃, took out the back and placed 6 days at 60 ℃, and visual observations sculpture goods no significant defect produces.
Embodiment 2
Make high temperature resistant silicon glued membrane tool according to a conventional method, spray copper powder, then use flame line spray to cast method spray to cast stainless steel layer, coat the polyester layer that following each composition mixes or combination is made again in parts by weight:
100 parts of unsaturated polyester resins
30 parts of pure aluminium silicate
2 parts of acryloxy ethyl phosphonic acid ester mixtures
5 parts of γ-Qiu Jibingjisanjiayangjiguiwans
Solidifying agent is an amount of
Promotor is an amount of
Anti-aging agent is an amount of,
Be added to certain required thickness gradually, cure and demold.Measure its metal level/non-metallic layer bond strength＞15MPa, the destructive test polyester layer destroys prior to joint.Measure metal level linear expansivity and polyester layer linear expansivity difference less than 2; The sculpture goods were placed 6 days at-18 ℃, took out the back and placed 6 days at 60 ℃, and visual observations sculpture goods no significant defect produces.
The comparative example 1
Press embodiment 1 described method, but coat the polyester layer that following each composition mixes or combination is made in parts by weight:
Unsaturated polyester resin: 100 parts,
Cyclohexanone peroxide 1.5-6 part, naphthoic acid cobalt 0.5-3 part, silicon powder 10-25 part is measured its metal level and non-metallic layer bond strength 6.7MPa, peel off earlier between destructive test metal level and the non-metallic layer, the linear expansivity difference is greater than 9 between metal level and the non-metallic layer.The sculpture goods were placed 6 days at-18 ℃, took out the back and placed 6 days at 60 ℃, and the visual observations sculpture goods line that fendillates produces.
The comparative example 2
Press embodiment 2 described methods, but coat the polyester layer that following each composition mixes or combination is made in parts by weight:
Unsaturated polyester resin: 100 parts,
Cyclohexanone peroxide 1.5-6 part, naphthoic acid cobalt 0.5-3 part, silicon powder 10-25 part is measured its metal level and non-metallic layer bond strength 4.6MPa, peel off earlier between destructive test metal level and the non-metallic layer, the linear expansivity difference is greater than 10 between metal level and the non-metallic layer.The sculpture goods were placed 6 days at-18 ℃, took out the back and placed 6 days at 60 ℃, and the visual observations sculpture goods line that fendillates produces.
Above embodiment just does comparatively detailed description to the present invention; be not used for limiting protection scope of the present invention; in the scope that does not break away from spirit of the present invention and design, those of ordinary skills can carry out various improvement or variation, still belong to protection scope of the present invention.
Claims (9)
1, the manufacture method of the high strength modified unsaturated polyester resin used of a kind of metal-polyester composite sculpture, following steps are arranged, it is characterized in that: continuing under the stirring condition earlier, in the resin compounded sculpture is filled a prescription with unsaturated polyester resin, add unsaturated phosphate coupling agent and silane coupling agent simultaneously, or add unsaturated phosphonic acid based coupling agent and silane coupling agent simultaneously; Add anti-aging agent again, then according to metal level metal types difference, select packing variety and ratio, so that the resin that has filler to fill is identical or close with the coefficient of expansion of metal level, thereby raising product strength, or by using the inorganic materials or the filler of following consumption, the coefficient of expansion that makes matrix material is identical with the coefficient of expansion of metallic substance or be close, continue to stir, obtain above-mentioned modified unsaturated polyester resin, standby, monoesters that above-mentioned unsaturated phosphate coupling agent is unsaturated phosphoric acid ester or dibasic acid esters or its mixture, above-mentioned phosphoric acid ester or the phosphonic acids usage quantity in unsaturated polyester resin are to use 0.01-10 weight % phosphoric acid ester or phosphonic acids in total unsaturated polyester resin weight; Above-mentioned inorganic materials or filler are selected from silicon-dioxide, lime carbonate, talcum powder, mica powder, pure aluminium silicate, aluminum oxide powder, stone material, one or both in glass fibre or other inorganic materials or two or more mixtures, or be selected from copper powder, aluminium powder, one or both of iron powder or other metal powder or two or more mixtures, the usage quantity of above-mentioned filler in resin is to use the above-mentioned filler of 20-35 weight % in total unsaturated polyester resin weight.
2, the manufacture method of the high strength modified unsaturated polyester resin used of metal-polyester composite sculpture as claimed in claim 1, it is characterized in that: said inorganic materials is a metal level, is copper, iron, the spray to cast layer of stainless steel or other metal or alloy, forge make the layer or electroformed layer in a kind of.
3, the manufacture method of the high strength modified unsaturated polyester resin used of metal-polyester composite sculpture as claimed in claim 1, it is characterized in that: described unsaturated phosphoric acid ester is the phosphoric acid ester that contains unsaturated link(age): acryloxy ethyl phosphonic acid ester, the methacryloxyethyl phosphoric acid ester, the acryloxy propyl phosphate, the methacryloxypropyl phosphoric acid ester; Two (acryloxy ethyl) phosphoric acid ester, two (methacryloxyethyl) phosphoric acid ester, two (acryloxy propyl group) phosphoric acid ester, one or both in two (methacryloxypropyl) phosphoric acid ester or two or more mixtures; Described insatiable hunger phosphonic acid based is the phosphonic acid based that contains unsaturated link(age): vinyl phosphonate, propenyl phosphonic acids, one or both in the isopropylene phosphonic acid or two or more mixtures.
4, the manufacture method of the high strength modified unsaturated polyester resin of using as claim 1 or 2 or 3 described metal-polyester composite sculptures, it is characterized in that: above-mentioned phosphoric acid ester or the phosphonic acids usage quantity in unsaturated polyester is for using above-mentioned phosphoric acid ester or the phosphonic acids of 0.01-5 weight % in total unsaturated polyester resin weight.
5, the manufacture method of the high strength modified unsaturated polyester resin used of metal-polyester composite sculpture as claimed in claim 4 is characterized in that: above-mentioned phosphoric acid ester or the phosphonic acids usage quantity in unsaturated polyester resin is for using above-mentioned phosphoric acid ester or the phosphonic acids of 0.1-3 weight % in total unsaturated polyester resin weight.
6, the manufacture method of the high strength modified unsaturated polyester resin used of metal-polyester composite sculpture as claimed in claim 5, it is characterized in that: above-mentioned silane coupling agent is variously can strengthen organism and inorganics bonded silicane material: vinyltrimethoxy silane, vinyltriethoxysilane or other vinyl alkoxy silane; Methyltrimethoxy silane, ethyl trimethoxy silane, butyl trimethoxy silane or other alkyl methoxy silane; γ-An Bingjisanjiayangjiguiwan, γ-An Bingjisanyiyangjiguiwan or other amino-contained silane; γ-acryloxy propyl trimethoxy silicane, γ-methacryloxypropyl trimethoxy silane, γ-acryloxy propyl group methyl dimethoxysilane, γ-acryloxy propyl group methyldiethoxysilane, γ-methacryloxypropyl methyldiethoxysilane or other γ-acryloxy propyl trialkoxy silane or γ-methacryloxypropyl trialkoxy silane or γ-acryloxy propyl group methyl dialkoxy silicane or γ-methacryloxypropyl methyl dialkoxy silicane; γ-Qiu Jibingjisanjiayangjiguiwan, γ-sulfydryl propyl-triethoxysilicane, γ-sulfydryl propyl group methyl dimethoxysilane, in γ-sulfydryl propyl group methyl dimethoxysilane or other γ-sulfydryl propyl group methyl methoxy base silane or γ-Qiu Jibingjisanjiayangjiguiwan or other silane coupling agent one or both or two or more mixtures, the usage quantity of above-mentioned silane coupling agent in unsaturated polyester resin are the above-mentioned silane coupling agent that uses 0.1-15 weight % in total unsaturated polyester material weight.
7, the manufacture method of the high strength modified unsaturated polyester resin used of metal-polyester composite sculpture as claimed in claim 6 is characterized in that: the usage quantity of above-mentioned silane coupling agent in unsaturated polyester resin is for using the above-mentioned silane coupling agent of 1-10 weight % in total unsaturated polyester weight.
8, the manufacture method of the high strength modified unsaturated polyester resin used of metal-polyester composite sculpture as claimed in claim 6 is characterized in that: the usage quantity of above-mentioned silane coupling agent in unsaturated polyester resin is for using the above-mentioned silane coupling agent of 1-5 weight % in total unsaturated polyester material weight.
9, the modified unsaturated polyester resin made of the manufacture method of the high strength modified unsaturated polyester resin of using as any described metal-polyester composite sculpture among claim 1-3, the 5-8, in bonding inorganic materials and inorganic materials, or the application in inorganic materials and the polyester.
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| CNB2005100850134A CN100475907C (en) | 2005-07-19 | 2005-07-19 | Manufacturing method and uses of modified unsaturated polyester resin for composite sculpture |
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| CNB2005100850134A CN100475907C (en) | 2005-07-19 | 2005-07-19 | Manufacturing method and uses of modified unsaturated polyester resin for composite sculpture |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102218963A (en) * | 2010-04-13 | 2011-10-19 | 台盐实业股份有限公司 | Composition of salt sculpture base material and manufacturing method thereof |
| CN102850828A (en) * | 2011-07-01 | 2013-01-02 | 湖南晟通科技集团有限公司 | Active nano silica composition and preparation method thereof |
| CN104945677A (en) * | 2015-06-26 | 2015-09-30 | 苏州荣昌复合材料有限公司 | Method for preparing high-temperature-resistant modified plastic |
-
2005
- 2005-07-19 CN CNB2005100850134A patent/CN100475907C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102218963A (en) * | 2010-04-13 | 2011-10-19 | 台盐实业股份有限公司 | Composition of salt sculpture base material and manufacturing method thereof |
| CN102850828A (en) * | 2011-07-01 | 2013-01-02 | 湖南晟通科技集团有限公司 | Active nano silica composition and preparation method thereof |
| CN102850828B (en) * | 2011-07-01 | 2016-08-17 | 晟通科技集团有限公司 | A kind of Active nano silica composition and preparation method thereof |
| CN104945677A (en) * | 2015-06-26 | 2015-09-30 | 苏州荣昌复合材料有限公司 | Method for preparing high-temperature-resistant modified plastic |
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| CN100475907C (en) | 2009-04-08 |
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Assignee: Zhejiang Condor sculpture craft Group Co., Ltd. Assignor: Cheng Yuquan|Fu Tiantian Contract fulfillment period: 2009.1.26 to 2019.1.25 contract change Contract record no.: 2009330000361 Denomination of invention: Manufacturing method and uses of modified unsaturated polyester resin for composite sculpture Granted publication date: 20090408 License type: Exclusive license Record date: 2009.2.24 |
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