CN102952257A - Method for preparing stereolithography rapid-prototyping photosensitive resin by adopting 1,4-cyclohexanedimethanol diglycidyl ether diacrylate as prepolymer - Google Patents
Method for preparing stereolithography rapid-prototyping photosensitive resin by adopting 1,4-cyclohexanedimethanol diglycidyl ether diacrylate as prepolymer Download PDFInfo
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- CN102952257A CN102952257A CN201210434978XA CN201210434978A CN102952257A CN 102952257 A CN102952257 A CN 102952257A CN 201210434978X A CN201210434978X A CN 201210434978XA CN 201210434978 A CN201210434978 A CN 201210434978A CN 102952257 A CN102952257 A CN 102952257A
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- photosensitive resin
- diglycidyl ether
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- ether diacrylate
- prepolymer
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- 229920005989 resin Polymers 0.000 title claims abstract description 78
- 239000011347 resin Substances 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 239000003822 epoxy resin Substances 0.000 claims abstract description 12
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 12
- 150000003254 radicals Chemical class 0.000 claims abstract description 10
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 7
- -1 oxetane compound Chemical class 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 12
- YQMXOIAIYXXXEE-UHFFFAOYSA-N 1-benzylpyrrolidin-3-ol Chemical compound C1C(O)CCN1CC1=CC=CC=C1 YQMXOIAIYXXXEE-UHFFFAOYSA-N 0.000 claims description 11
- YVTVFZKHLXIJEY-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.C1OC1COCC1CO1 Chemical compound OC(=O)C=C.OC(=O)C=C.C1OC1COCC1CO1 YVTVFZKHLXIJEY-UHFFFAOYSA-N 0.000 claims description 11
- 125000002091 cationic group Chemical group 0.000 claims description 7
- 125000003566 oxetanyl group Chemical group 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 3
- 239000011353 cycloaliphatic epoxy resin Substances 0.000 claims description 3
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- 239000012955 diaryliodonium Substances 0.000 claims 3
- 125000005520 diaryliodonium group Chemical group 0.000 claims 3
- 125000005409 triarylsulfonium group Chemical group 0.000 claims 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims 2
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 claims 1
- 229930185605 Bisphenol Natural products 0.000 claims 1
- 244000028419 Styrax benzoin Species 0.000 claims 1
- 235000000126 Styrax benzoin Nutrition 0.000 claims 1
- 235000008411 Sumatra benzointree Nutrition 0.000 claims 1
- BDAHDQGVJHDLHQ-UHFFFAOYSA-N [2-(1-hydroxycyclohexyl)phenyl]-phenylmethanone Chemical compound C=1C=CC=C(C(=O)C=2C=CC=CC=2)C=1C1(O)CCCCC1 BDAHDQGVJHDLHQ-UHFFFAOYSA-N 0.000 claims 1
- DBHQYYNDKZDVTN-UHFFFAOYSA-N [4-(4-methylphenyl)sulfanylphenyl]-phenylmethanone Chemical compound C1=CC(C)=CC=C1SC1=CC=C(C(=O)C=2C=CC=CC=2)C=C1 DBHQYYNDKZDVTN-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229960002130 benzoin Drugs 0.000 claims 1
- 150000008366 benzophenones Chemical class 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000012682 free radical photopolymerization Methods 0.000 claims 1
- 235000019382 gum benzoic Nutrition 0.000 claims 1
- 239000004843 novolac epoxy resin Substances 0.000 claims 1
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 5
- 206010034972 Photosensitivity reaction Diseases 0.000 abstract description 5
- 230000036211 photosensitivity Effects 0.000 abstract description 5
- 150000001768 cations Chemical class 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 21
- 238000007493 shaping process Methods 0.000 description 17
- 238000007711 solidification Methods 0.000 description 14
- 230000008023 solidification Effects 0.000 description 14
- 229940106691 bisphenol a Drugs 0.000 description 13
- 239000004593 Epoxy Substances 0.000 description 10
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 8
- GXGJIOMUZAGVEH-UHFFFAOYSA-N Chamazulene Chemical group CCC1=CC=C(C)C2=CC=C(C)C2=C1 GXGJIOMUZAGVEH-UHFFFAOYSA-N 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 6
- 150000004702 methyl esters Chemical class 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 230000035939 shock Effects 0.000 description 5
- CWXZAJNUTOBAOI-UHFFFAOYSA-N 1-(2,3-dimethoxyphenyl)-2-hydroxy-2-phenylethanone Chemical compound COC1=CC=CC(C(=O)C(O)C=2C=CC=CC=2)=C1OC CWXZAJNUTOBAOI-UHFFFAOYSA-N 0.000 description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 description 4
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 235000019633 pungent taste Nutrition 0.000 description 3
- 150000005839 radical cations Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 2
- 229940000489 arsenate Drugs 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000004043 responsiveness Effects 0.000 description 2
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000011089 mechanical engineering Methods 0.000 description 1
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 150000002921 oxetanes Chemical class 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
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- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
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- Epoxy Resins (AREA)
Abstract
The present invention discloses a method for application of 1,4-cyclohexanedimethanol diglycidyl ether diacrylate as an acrylate prepolymer in stereolithography rapid-prototyping photosensitive resin preparation. The prepared photosensitive resin mainly comprises the following raw material components, by mass, 15-65 parts of 1,4-cyclohexanedimethanol diglycidyl ether diacrylate, 5-55 parts of an epoxy resin, 5-55 parts of trimethylene oxide, 1-12 parts of a cation type photopolymerization initiator, and 1-10 parts of a free radical type photopolymerization initiator. The prepared photosensitive resin has good photosensitivity and a critical exposure amount Ec of less than 16.0 mJ/cm<2>. After the photosensitive resin is subjected to stereolithography prototyping, precision of the prototyping part is high, a buckling factor CF (6) of the prototyping part is within a range of +-0.01, and CF (11) of the prototyping part is within a range of +-0.03. With the prepared photosensitive resin, parts with any complex shapes and high precision can be directly manufactured. In addition, the 1,4-cyclohexanedimethanol diglycidyl ether diacrylate has characteristics of moderate viscosity, low odor and good cured product flexibility, such that the 1,4-cyclohexanedimethanol diglycidyl ether diacrylate can be adopted as an acrylate prepolymer to replace a bisphenol A type epoxy acrylate to be applied in stereolithography rapid-prototyping photosensitive resin prepartion.
Description
Technical field
The present invention relates to a kind of method for preparing stereolithography rapid shaping photosensitive resin, relate in particular to a kind of 1,4 cyclohexane dimethanol diglycidyl ether diacrylate prepares stereolithography rapid shaping photosensitive resin as prepolymer method and application.
Background technology
The stereolithography rapid shaping is a kind of rapid shaping technique that occurs the earliest.It makes principle based on entity layering, take photosensitive resin as raw material, by the Ultra-Violet Laser edge minute layer cross section point by point scanning under the CNC control, make thin resin layer in the scanning area produce photopolymerization reaction and solidify, thereby form a cross section thin layers of product, the vertical interlock of cooperating platform, the lower one deck resin of scanning, new one deck that solidifies is bonded on front one deck securely, successively piles up so successively, forms physical prototype.Remove support, carry out aftertreatment, namely obtain required entity prototype.Because the stereolithography rapid shaping is take photosensitive resin as starting material, therefore the characteristic of photosensitive resin directly affects performance, forming speed and the final precision etc. of product.Stereolithography rapid shaping photosensitive resin before nineteen ninety-five mainly is with epoxy acrylate and the urethane acrylate free radical type photosensitive resin as prepolymer.Advantages such as it is cheap that although this type free fundamental mode photosensitive resin has, and solidification rate is fast, because cure shrinkage is serious, the product warpage is obvious, and precision is difficult to meet the demands, and finally is eliminated.
Now, foreign applications mainly is that free radical-cation type mixes type photosensitive resin in the photosensitive resin of stereolithography rapid shaping, and the characteristics of this photosensitive resin are that prepolymer not only contains bisphenol-a epoxy acrylate but also contain Resins, epoxy usually.This photosensitive resin has been concentrated the advantage that the acrylate curing speed is fast and the epoxy resin cure contraction is little, and making it this photosensitive resin, both to have had photosensitivity good, has again high characteristics of profiled member precision.For example, the photosensitive resin of the photosensitive resin of U.S. Huntsman company and DSM SOMOS company just belongs to free radical-cation type and mixes type photosensitive resin, their free radical type esters of acrylic acid prepolymer mainly is bisphenol-a epoxy acrylate, see US Patent No.: 6365644, US:5707780, US:5525645, US:5573889 and US:5665792, and do not relate to the application of 1,4 cyclohexane dimethanol diglycidyl ether diacrylate.
At home, many universities and R﹠D institution are arranged also in the research of carrying out stereolithography rapid shaping photosensitive resin, obtained some achievements.For example, cloudy gold perfume, Liu Guowen, Meng Huaidong and Hong Xiaoyin have delivered " the photosensitive resin of free radical that is used for stereolithography is studied and used " paper in the 3rd phase of 1998 " radiation research and radiation process journal ".Duan Yugang, Wang Suqin, Li Dichen, Lu Bingheng and Wang Xuerang calendar year 2001 " XI AN JIAOTONG UNIVERSITY Subject Index " o. 11th delivered " a kind of research of the low warpage photosensitive resin for the laser curing Quick-forming " paper.Yang Yuanli, Wang Yongzhen and Wang Ailing have delivered " preparation of Stereo Lithography Materials " paper " mechanical engineering material " the 2nd phase in 2007.Guangzhou Inst. of Machinery Science Haitao Liu, Zhong Hanrong and Xue Jidong have proposed " a kind of stereolithography rapid prototyping photosensitive resin and its preparation method and application ", and the number of applying for a patent is CN200910040526.1.The king of Zhejiang Polytechnical University sea moral, Malaysian outstanding person, Sun Xingping wait to have proposed " a kind of UV curing photosensitive resin for rapid moulding injection mold ", and the number of applying for a patent is CN200910095846.7.But, in paper and issued patents that these are delivered, they prepare the used esters of acrylic acid prepolymer of photosensitive resin and also are mainly bisphenol-a epoxy acrylate, all also do not relate to as stereolithography rapid shaping photosensitive resin prepolymer for using the 1,4 cyclohexane dimethanol diglycidyl ether diacrylate.
Summary of the invention
The purpose of this invention is to provide a kind of 1,4-cyclohexanedimethanodiglycidyl diglycidyl ether diacrylate prepares the method for stereolithography rapid shaping photosensitive resin as prepolymer, little volatility, little and the viscosity of pungency moderate 1,4-cyclohexanedimethanodiglycidyl diglycidyl ether diacrylate prepares stereolithography rapid shaping photosensitive resin as a kind of prepolymer, and need not to add the larger bisphenol-a epoxy acrylate of viscosity, while can avoid adding volatility greatly and the larger thinner Viscoat 295 of pungency, tripropylene glycol diacrylate and 1,6 hexanediol diacrylate etc.
The present invention is achieved through the following technical solutions.Its chemical structural formula of 1,4 cyclohexane dimethanol diglycidyl ether diacrylate of the present invention:
Stereolithography rapid shaping photosensitive resin of the present invention is comprised of the raw material of following parts by weight:
15～65 parts of 1,4 cyclohexane dimethanol diglycidyl ether diacrylates;
5～55 parts of Resins, epoxy;
5～55 parts of oxetane compounds;
1～12 part of cationic initiator;
1～10 part free radical type Photoepolymerizationinitiater initiater.
Resins, epoxy of the present invention comprises bisphenol A type epoxy resin, phenol aldehyde type epoxy resin, cycloaliphatic epoxy resin etc., or their several mixtures.Preferably, select cycloaliphatic epoxy resin, for example, 3,4-epoxycyclohexyl formic acid-3
', 4
'-epoxycyclohexyl methyl esters.
Oxetane compound of the present invention refers to contain a series of organism of oxetane groups, and it comprises the serial organism that contains an oxetane groups and two oxetane groups.Preferably, select to contain the serial organism of two oxetane groups, for example, 3,3-[oxygen base dimethylene]-two [3-ethyl] trimethylene oxide.
Cationic initiator of the present invention comprises salt compounded of iodine and sulfonium salt, wherein mainly refers to diaryl iodine hexafluorophosphate, diaryl iodine hexafluoro arsenate, diaryl iodine hexafluoro antimonate and triaryl matte hexafluorophosphate, triaryl matte hexafluoro arsenate, triaryl matte hexafluoro antimonate etc.Preferably, select the triaryl matte hexafluoro antimonate.
Free radical type initiator of the present invention comprises can cause the free radical type initiator that all unsaturated monomers that contain the two keys of carbon carry out polymerization.For example, benzophenone, dimethoxybenzoin, diphenyl antimony chloride ketone, 4-benzoyl-4
'-dimethyl diphenyl sulfide, 2-hydroxy-2-methyl-1-phenyl-1-acetone, 1-hydroxy cyclohexyl phenylketone and 2,4-diethyl thioxanthone, perhaps both or both above mixture in them.Preferably, select dimethoxybenzoin and 1-hydroxy cyclohexyl phenylketone.
Preparation method of the present invention is that described material component is mixed by described parts by weight proportioning; Then, heating, stirring namely 20～80 ℃ of temperature, were stirred 5～120 minutes, made it to become transparent faint yellow uniform liquid.
Ultimate principle of the present invention is as follows: now, popular stereolithography rapid shaping photosensitive resin is that free radical-cation type mixes type photosensitive resin on the domestic and international market, the prepolymer of contained free radical type part bisphenol-a epoxy acrylate normally wherein, the prepolymer of cationic part is Resins, epoxy and trimethylene oxide normally.The bisphenol-a epoxy acrylate prepolymer is because viscosity is larger, cured article fragility is large, usually need to add acrylate monomer, as: Viscoat 295, tripropylene glycol diacrylate and 1,6-hexanediyl ester etc., the performance of regulating viscosity and cured article as thinner.Therefore, select the low smell of viscosity Shi Zhong ﹑ and the good esters of acrylic acid prepolymer of cured article snappiness to seem extremely important, and 1,4-cyclohexanedimethanodiglycidyl diglycidyl ether diacrylate has above-mentioned characteristics, can consider to select it to prepare stereolithography rapid shaping photosensitive resin as the free radical type part prepolymer of photosensitive resin.
Has less shrinkability when solidifying for the stereolithography rapid shaping photosensitive resin that makes preparation, product has higher precision, the present invention adopts Resins, epoxy, trimethylene oxide or their mixture as prepolymer for the contained cationic part of photosensitive resin, because the polymerization of Resins, epoxy, trimethylene oxide is ring-opening polymerization, shrink little.
The polymerization of 1,4 cyclohexane dimethanol diglycidyl ether diacrylate is the polymerization that the two bond ruptures of carbon become singly-bound, shrinks greatly.Yet, for the photosensitive resin that makes preparation has preferably photosensitivity, need to adopt as much as possible 1,4-cyclohexanedimethanodiglycidyl diglycidyl ether diacrylate prepolymer is as raw material, use less Resins, epoxy, trimethylene oxide as raw material, because 1,4 cyclohexane dimethanol diglycidyl ether diacrylate prepolymer under UV-irradiation its solidification rate faster than the solidification rate of Resins, epoxy and trimethylene oxide.In order to make photosensitive resin can keep high precision when the product and to take into account the photosensitivity of photosensitive resin, during the preparation photosensitive resin, add-on for Resins, epoxy, trimethylene oxide and 1,4 cyclohexane dimethanol diglycidyl ether diacrylate is reasonably combined.In addition, the present invention also selects ultraviolet initiator.Not only selected the free radical type initiator of initiating methacrylates polymerization but also selected to cause the cationic initiator of Resins, epoxy and trimethylene oxide polymerization.When selecting initiator, to notice considering that initiator has preferably responsiveness to the specific wavelength UV-light that ultraviolet laser sends, namely the 355nm UV-light be had preferably responsiveness.
The present invention has following beneficial effect: with respect to commercialization photosensitive resin in the past, its principal feature of photosensitive resin of the present invention's preparation is: (1) is owing to being to add 1,4-cyclohexanedimethanodiglycidyl diglycidyl ether diacrylate is as the esters of acrylic acid prepolymer, so need not to add again prepolymer and the acrylate thinners such as bisphenol-a epoxy acrylate, phenolic epoxy acrylate and pentaerythritol triacrylate, like this so that the photosensitive resin pungency of preparation is little and volatile matter is few, simultaneously, make the step of preparation photosensitive resin become more easy.(2) good as the photosensitivity of the photosensitive resin of esters of acrylic acid prepolymer preparation with the 1,4 cyclohexane dimethanol diglycidyl ether diacrylate, its critical exposure E
cLess than 16.0mJ/cm
2(3) precision of forming part is high, and the warp factor CF of forming part (6) is in ± 0.01 scope, and CF (11) is in ± 0.03 scope.(4) mechanical property of forming part is better.
Adopt the photosensitive resin of the present invention's preparation can directly produce any complicated shape, have a high-precision part, and the preparation cost valency of this photosensitive resin is about 260 yuan of per kilogram, far below the selling price (approximately 1500 yuans of per kilograms) of the photosensitive resin of Huntsman company and DSM SOMOS company.
Embodiment
Below in conjunction with embodiment, the present invention is done further detailed description, but implementation of the present invention is not limited to this.
Embodiment 1
1. in the special 5000 milliliters glass there-necked flask of agitator and prolong is housed, add 3,4-epoxycyclohexyl formic acid-3
,, 4
,-epoxycyclohexyl methyl esters 1000 grams, 3,3-[oxygen base dimethylene]-two [3-ethyl] trimethylene oxide 500 grams, bisphenol A type epoxy resin (E-51) 500 grams, 1,4-cyclohexanedimethanodiglycidyl diglycidyl ether diacrylate 730 grams, dimethoxybenzoin 100 grams, triaryl matte hexafluoro antimonate 170 grams.
2. be heated to 50 ℃, stirred 30 minutes, make it to become transparent faint yellow uniform liquid, this liquid is a kind of photosensitive resin of preparation.Record its critical exposure E
cBe 15.1mJ/cm
2
Critical exposure E
cTesting method be adopt " Zhao Yi. the experimental study of photosensitive resin characteristic [J] in the laser fast forming. polymer material science and engineering, 2004,20(1): 184-186 " method reported.
3. the SLA-3500 type ultraviolet laser solidification rapid forming equipment that utilizes 3D Systems company to make has been made some test blocks, then, is in the 500 milliwatt ultraviolet casees at power, these test blocks of after fixing 90 minutes.Record their warp factor CF (6)=0.01, CF (11)=0.02.
For ultraviolet laser solidification rapid shaping photosensitive resin make the precision evaluation standard of part existing popular be the warp factor evaluation method, what its method adopted is the method for formulating in the international Quick-forming meeting of Second Committee of holding in 1991.
4. utilizing SLA-3500 type ultraviolet laser solidification rapid forming equipment, made some test blocks according to ASTM D638 and ASTM D256 standard, then, is in the 500 milliwatt ultraviolet casees at power, these test blocks of after fixing 90 minutes.Record their tensile strength 30.7MP
a, Young's modulus 1209.5MP
a, elongation at break 15.3% and resistance to impact shock 29.8J/m.
Embodiment 2
1. in the special 5000 milliliters glass there-necked flask of agitator and prolong is housed, add 3,4-epoxycyclohexyl formic acid-3
,, 4
,-epoxycyclohexyl methyl esters 900 grams, bisphenol A type epoxy resin (E-51) 600 grams, 3,3-[oxygen base dimethylene]-two [3-ethyl] trimethylene oxide 400 grams, 1,4-cyclohexanedimethanodiglycidyl diglycidyl ether diacrylate 800 grams, 2-hydroxy-2-methyl-1-phenyl-1-acetone 110 grams, triaryl matte hexafluoro antimonate 190 grams.
2. be heated to 40 ℃, stirred 30 minutes, make it to become transparent faint yellow uniform liquid, this liquid is a kind of photosensitive resin of preparation.Record its critical exposure E
cBe 14.9 mJ/cm
2
3. utilizing SLA-3500 type ultraviolet laser solidification rapid forming equipment to make some test blocks, then, is in the 500 milliwatt ultraviolet casees at power, these test blocks of after fixing 90 minutes.Record their warp factor CF (6)=-0.01, CF (11)=-0.02.
4. utilizing SLA-3500 type ultraviolet laser solidification rapid forming equipment, made some test blocks according to ASTM D638 and ASTM D256 standard, then, is in the 500 milliwatt ultraviolet casees at power, these test blocks of after fixing 90 minutes.Record their tensile strength 29.1 MP
a, Young's modulus 1155.6MP
a, elongation at break 19.1% and resistance to impact shock 31.4J/m.
Embodiment 3
1. in the special 5000 milliliters glass there-necked flask of agitator and prolong is housed, add 3,4-epoxycyclohexyl formic acid-3
,, 4
,-epoxycyclohexyl methyl esters 500 grams, bisphenol A type epoxy resin (E-51) 900 grams, 3,3-[oxygen base dimethylene]-two [3-ethyl] trimethylene oxide 400 grams, 1,4-cyclohexanedimethanodiglycidyl diglycidyl ether diacrylate 900 grams, dimethoxybenzoin 100 grams, triaryl matte hexafluoro antimonate 200 grams.
2. be heated to 50 ℃, stirred 20 minutes, make it to become transparent faint yellow uniform liquid, this liquid is a kind of photosensitive resin of preparation.Record its critical exposure E
cBe 15.3mJ/cm
2
3. utilizing SLA-3500 type ultraviolet laser solidification rapid forming equipment to make some test blocks, then, is in the 500 milliwatt ultraviolet casees at power, these test blocks of after fixing 90 minutes.Record their warp factor CF (6)=-0.01, CF (11)=-0.03.
4. utilizing SLA-3500 type ultraviolet laser solidification rapid forming equipment, made some test blocks according to ASTM D638 and ASTM D256 standard, then, is in the 500 milliwatt ultraviolet casees at power, these test blocks of after fixing 90 minutes.Record their tensile strength 24.9MP
a, Young's modulus 1103.8MP
a, elongation at break 22.7 % and resistance to impact shock 36.3J/m.
Embodiment 4
1. in the special 5000 milliliters glass there-necked flask of agitator and prolong is housed, add 3,4-epoxycyclohexyl formic acid-3
,, 4
,-epoxycyclohexyl methyl esters 1500 grams, bisphenol A type epoxy resin (E-51) 300 grams, 3,3-[oxygen base dimethylene]-two [3-ethyl] trimethylene oxide 330 grams, 1,4-cyclohexanedimethanodiglycidyl diglycidyl ether diacrylate 600 grams, 1-hydroxy cyclohexyl phenylketone 90 grams, triaryl matte hexafluoro antimonate 180 grams.
2. be heated to 35 ℃, stirred 60 minutes, make it to become transparent faint yellow uniform liquid, this liquid is a kind of photosensitive resin of preparation.Record its critical exposure E
cBe 14.1 mJ/cm
2
3. utilizing SLA-3500 type ultraviolet laser solidification rapid forming equipment to make some test blocks, then, is in the 500 milliwatt ultraviolet casees at power, these test blocks of after fixing 90 minutes.Record their warp factor CF (6)=-0.01, CF (11)=0.01.
4. utilizing SLA-3500 type ultraviolet laser solidification rapid forming equipment, made some test blocks according to ASTM D638 and ASTM D256 standard, then, is in the 500 milliwatt ultraviolet casees at power, these test blocks of after fixing 90 minutes.Record their tensile strength 34.2MP
a, Young's modulus 1356.7MP
a, elongation at break 12.2% and resistance to impact shock 26.4J/m.
Embodiment 5
1. in the special 5000 milliliters glass there-necked flask of agitator and prolong is housed, add 3,4-epoxycyclohexyl formic acid-3
,, 4
,-epoxycyclohexyl methyl esters 1700 grams, bisphenol A type epoxy resin (E-51) 400 grams, 3,3-[oxygen base dimethylene]-two [3-ethyl] trimethylene oxide 450 grams, 1,4-cyclohexanedimethanodiglycidyl diglycidyl ether diacrylate 200 grams, 1-hydroxy cyclohexyl phenylketone 100 grams, triaryl matte hexafluoro antimonate 150 grams.
2. be heated to 65 ℃, stirred 10 minutes, become transparent faint yellow uniform liquid, this liquid is a kind of photosensitive resin of preparation.Record its critical exposure E
cBe 15.7 mJ/cm
2
3. utilizing SLA-3500 type ultraviolet laser solidification rapid forming equipment to make some test blocks, then, is in the 500 milliwatt ultraviolet casees at power, these test blocks of after fixing 90 minutes.Record their warp factor CF (6)=0.01, CF (11)=0.02.
4. utilizing SLA-3500 type ultraviolet laser solidification rapid forming equipment, made some test blocks according to ASTM D638 and ASTM D256 standard, then, is in the 500 milliwatt ultraviolet casees at power, these test blocks of after fixing 90 minutes.Record their tensile strength 35.9MP
a, Young's modulus 1472.2MP
a, elongation at break 9.5% and resistance to impact shock 23.2J/m.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from spirit of the present invention with away from the lower change of making, modification, substitute, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (6)
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Cited By (4)
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| CN104892549A (en) * | 2015-04-20 | 2015-09-09 | 南昌大学 | Synthesis method of allyl oxetane compound for ultraviolet light curing |
| CN106221177A (en) * | 2016-07-26 | 2016-12-14 | 苏州秉创科技有限公司 | A kind of injecting type 3D prints photo-curing material |
| CN107382719A (en) * | 2017-06-23 | 2017-11-24 | 武汉长盈鑫科技有限公司 | A kind of preparation method of anhydride modified biphenyl oxetanes acrylic ester prepolymer |
| CN108485184A (en) * | 2018-02-11 | 2018-09-04 | 东莞爱的合成材料科技有限公司 | One kind can be used for clinical medical thermostable transparent photosensitive resin and preparation method thereof |
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| CN102439145A (en) * | 2009-04-24 | 2012-05-02 | 帝斯曼知识产权资产管理有限公司 | Polypeptides for degrading carbohydrates and uses thereof |
| CN102432840A (en) * | 2011-10-25 | 2012-05-02 | 南昌大学 | Stereolithography rapid prototyping photosensitive resin prepared by taking polypropylene glycol diglycidyl ether diacrylate as prepolymer and preparation method |
| CN102584578A (en) * | 2012-01-06 | 2012-07-18 | 南昌大学 | Preparation method and application of 1,4-cyclohexanedimethanol diglycidyl ether diacrylate |
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| EP0848294A1 (en) * | 1996-12-13 | 1998-06-17 | Dsm N.V. | Photo-curable resin composition used for photo-fabrication of three-dimensional objects |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104892549A (en) * | 2015-04-20 | 2015-09-09 | 南昌大学 | Synthesis method of allyl oxetane compound for ultraviolet light curing |
| CN106221177A (en) * | 2016-07-26 | 2016-12-14 | 苏州秉创科技有限公司 | A kind of injecting type 3D prints photo-curing material |
| CN107382719A (en) * | 2017-06-23 | 2017-11-24 | 武汉长盈鑫科技有限公司 | A kind of preparation method of anhydride modified biphenyl oxetanes acrylic ester prepolymer |
| CN107382719B (en) * | 2017-06-23 | 2020-07-14 | 武汉长盈鑫科技有限公司 | A kind of preparation method of acid anhydride modified biphenyl oxetane acrylate prepolymer |
| CN108485184A (en) * | 2018-02-11 | 2018-09-04 | 东莞爱的合成材料科技有限公司 | One kind can be used for clinical medical thermostable transparent photosensitive resin and preparation method thereof |
| CN108485184B (en) * | 2018-02-11 | 2020-11-24 | 东莞爱的合成材料科技有限公司 | A kind of high temperature resistant transparent photosensitive resin which can be used in clinical medicine and preparation method thereof |
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Application publication date: 20130306 |