CN105068378A - Flame-retardant stereo lithography apparatus (SLA) photosensitive resin for three-dimensional (3D) printing - Google Patents
Flame-retardant stereo lithography apparatus (SLA) photosensitive resin for three-dimensional (3D) printing Download PDFInfo
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- CN105068378A CN105068378A CN201510463866.0A CN201510463866A CN105068378A CN 105068378 A CN105068378 A CN 105068378A CN 201510463866 A CN201510463866 A CN 201510463866A CN 105068378 A CN105068378 A CN 105068378A
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- acrylate
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- phosphorus
- prepolymer
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- 239000011347 resin Substances 0.000 title claims abstract description 52
- 229920005989 resin Polymers 0.000 title claims abstract description 52
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000003063 flame retardant Substances 0.000 title claims abstract description 27
- 238000001459 lithography Methods 0.000 title abstract 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 60
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 39
- 239000011574 phosphorus Substances 0.000 claims abstract description 39
- 239000003085 diluting agent Substances 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims description 29
- 239000003112 inhibitor Substances 0.000 claims description 29
- 238000006116 polymerization reaction Methods 0.000 claims description 29
- -1 hydroxyl acrylate compound Chemical class 0.000 claims description 26
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 239000012752 auxiliary agent Substances 0.000 claims description 15
- 239000003729 cation exchange resin Substances 0.000 claims description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 13
- 239000002518 antifoaming agent Substances 0.000 claims description 13
- 229920000570 polyether Polymers 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 11
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 10
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 8
- VHSHLMUCYSAUQU-UHFFFAOYSA-N 2-hydroxypropyl methacrylate Chemical compound CC(O)COC(=O)C(C)=C VHSHLMUCYSAUQU-UHFFFAOYSA-N 0.000 claims description 8
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 8
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 8
- KEQFTVQCIQJIQW-UHFFFAOYSA-N N-Phenyl-2-naphthylamine Chemical compound C=1C=C2C=CC=CC2=CC=1NC1=CC=CC=C1 KEQFTVQCIQJIQW-UHFFFAOYSA-N 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 7
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 7
- 229920000728 polyester Polymers 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- 238000010146 3D printing Methods 0.000 claims description 6
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 claims description 6
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 6
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 6
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 5
- 229940023913 cation exchange resins Drugs 0.000 claims description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 claims description 4
- 150000003254 radicals Chemical class 0.000 claims description 4
- XESZUVZBAMCAEJ-UHFFFAOYSA-N 4-tert-butylcatechol Chemical compound CC(C)(C)C1=CC=C(O)C(O)=C1 XESZUVZBAMCAEJ-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- LFMAOMQWCSTELR-UHFFFAOYSA-N 2-methyl-2-oxo-1,2$l^{5}-oxaphospholan-5-one Chemical compound CP1(=O)CCC(=O)O1 LFMAOMQWCSTELR-UHFFFAOYSA-N 0.000 claims description 2
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 claims description 2
- PGDIJTMOHORACQ-UHFFFAOYSA-N 9-prop-2-enoyloxynonyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCOC(=O)C=C PGDIJTMOHORACQ-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- 239000000470 constituent Substances 0.000 abstract 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 16
- 229910052710 silicon Inorganic materials 0.000 description 16
- 239000010703 silicon Substances 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000012949 free radical photoinitiator Substances 0.000 description 10
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 9
- 238000000926 separation method Methods 0.000 description 8
- 239000013530 defoamer Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920002635 polyurethane Polymers 0.000 description 6
- 239000004814 polyurethane Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- NSFGOWGWLHAJPC-UHFFFAOYSA-N COCOC.C(C=C)(=O)O Chemical compound COCOC.C(C=C)(=O)O NSFGOWGWLHAJPC-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- BHTGWFPRDIDXJT-UHFFFAOYSA-N CC(C(CCC1)[ClH]C1=N)N Chemical compound CC(C(CCC1)[ClH]C1=N)N BHTGWFPRDIDXJT-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- BHHGXPLMPWCGHP-UHFFFAOYSA-N Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical class OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a flame-retardant stereo lithography apparatus (SLA) photosensitive resin for three-dimensional (3D) printing. The flame-retardant SLA photosensitive resin is characterized by comprising the following constituents by weight: 15-75% of phosphorus-containing acrylate prepolymer, 15-75% of acrylate, 1-5% of radical initiator, 0.5-2% of auxiliary and 5-15% of reactive diluents, the sum of the weight percentages of all constituents is 100%, the structural formula of the phosphorus-containing acrylate prepolymer is as shown in the specification, wherein R1 is (H2C=CH-) or a group as shown in the specification, and R2 is one of (-CH2-CH2-), a group as shown in the specification and (-CH2-CH2-CH2-CH2-).
Description
Technical Field
The invention relates to the technical field of 3D printing, in particular to SLA flame-retardant photosensitive resin for 3D printing.
Background
Stereolithography is a process that uses the principles of Stereolithography (SLA), the earliest rapid prototyping technology that has emerged as the most mature and widely used technology, introduced by 3d systems of america in the late 20 th century and the 80 th decade. The SLA forming method is that liquid photosensitive resin is filled in a resin liquid tank and is rapidly solidified under the irradiation of laser beams, when the forming process starts, a lifting workbench is positioned at the height of one section layer thickness below a liquid level, focused laser beams are controlled by a computer to scan along the liquid level according to the requirements of section profiles, and the resin in a scanned area is solidified, so that the plastic sheet with the section profiles is obtained. The table is then lowered by one sheet height and the cured plastic sheet is capped with a new layer of liquid resin for a second laser scanning cure, the newly cured layer firmly clinging to the previous layer, and so on until the entire product is formed. Because of the advantages of the SLA technology, such as high curing speed, high production efficiency, suitability for industrial flow line production and the like, the SLA photosensitive resin is increasingly applied in the rapid prototyping manufacturing industry in large quantity. The SLA photosensitive resin needs to have the following characteristics: the viscosity is low, the fluidity is good, and the resin leveling is facilitated; the curing speed is high, the forming efficiency is directly influenced by the curing speed, and the economic benefit is indirectly influenced; the shrinkage during curing is small, and the shrinkage can be generated in the curing process of the liquid resin, so that the cured parts are warped and deformed, and the molding precision is influenced.
Although the photosensitive resin used in the SLA technology can satisfy the above characteristics, most of the photosensitive resin is flammable, and with the rapid development and large-scale application of the SLA technology, the disadvantage of the photosensitive resin inevitably limits the application range and hinders the development of the whole industry. If a flame retardant derived from phosphorus oxychloride used as a raw material is added into an SLA photosensitive resin system by a conventional means, although the flame retardant problem can be partially solved, the phosphorus oxychloride in the production has high toxicity, HCl can be decomposed, the environment is polluted, and the flame retardant used as an external flame retardant has certain problems in compatibility with the SLA photosensitive resin. Therefore, development of SLA photosensitive resins having bulk flame retardant properties is of great significance.
Disclosure of Invention
The invention aims to solve the defects of the background technology and provide a non-toxic and environment-friendly flame-retardant SLA photosensitive resin for 3D printing.
The technical scheme of the invention is as follows: the flame-retardant SLA photosensitive resin for 3D printing is characterized by comprising the following components in percentage by weight: 15-75% of phosphorus-containing acrylate prepolymer, 15-75% of acrylate, 1-5% of free radical initiator, 0.5-2% of auxiliary agent and 5-15% of reactive diluent, wherein the sum of the weight percentages of the components is 100%; the structural general formula of the phosphorus-containing acrylate prepolymer is
Wherein,
R1＝H2c ═ CH-or
R2＝——CH2-CH2——、or-CH2-CH2-CH2-CH2-one of the above.
Preferably, the phosphorus-containing acrylate prepolymer is obtained by mixing 2-methyl-2, 5-dioxo-1, 2-Oxyphospholane (OP) and hydroxyl acrylate compounds in a molar ratio of 1:1, adding a catalyst and a polymerization inhibitor, and reacting for 5-6h at the temperature of 110-130 ℃;
the hydroxyl acrylic ester compound is one of hydroxyethyl acrylate, beta-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, hydroxyethyl methacrylate and beta-hydroxypropyl methacrylate.
Further, the polymerization inhibitor is one or a combination of more of hydroquinone, p-hydroxyanisole, p-benzoquinone, N-phenyl-2-naphthylamine and p-tert-butyl catechol, and the dosage of the polymerization inhibitor is 0.1-5.0% of the sum of the mass of the 2-methyl-2, 5-dioxo-1, 2-oxyphospholane OP and the mass of the hydroxyacrylate compound.
Further, the catalyst is one or a combination of more of strong acid cation exchange resins PK208LH, PK212LH, RCP106M, D001 and NKC-9, and the dosage of the catalyst is 5-8% of the sum of the mass of the 2-methyl-2, 5-dioxo-1, 2-oxyphospholane OP and the mass of the hydroxyacrylate compound. PK208LH, PK212LH and RCP106M are strong-acid cation exchange resins produced by Mitsubishi chemistry, and D001 and NKC-9 are strong-acid cation exchange resins produced by resin works of Tianjin university.
Preferably, the acrylate is one or a combination of aliphatic urethane acrylate, aromatic urethane acrylate, epoxy acrylate or polyester acrylate. The acrylate may be selected from aliphatic urethane acrylate of Changxing company of Taiwan: 6141H-80, 6148J-75, 615-100, 6151, 6153-3, 6157B-80, 6168, 6170, DR-U356, DR-U390; aromatic urethane acrylate of Changxing company: 6146-100; epoxy acrylate from Changxing corporation: 6202. 622A-80, 623-100, 624A-45, 625C-45; polyester acrylate of Changxing company: 6315. 6320, 6351, 6371, 6390F.
Preferably, the free radical initiator comprises one or more of photoinitiators 1173, 184, 907, 369, 651, 819 and ITX. Photoinitiators 1173, 184, 907, 369, 651, 819 and ITX are all conventional initiators in the prior art.
Preferably, the reactive diluent is one or a combination of more of functional acrylate monomer 2- (1, 2-cyclohexane-1, 2-dicarboximide) ethyl acrylate, cyclotrimethylolpropane formal acrylate, 2-phenoxyethyl acrylate, isobornyl acrylate, cyclohexyl methacrylate, dipropylene glycol diacrylate and 1, 9-nonanediol diacrylate. The reactive diluent can be selected from functional acrylate monomers of Taiwan Changxing company: EM21402- (1, 2-cyclohexane-1, 2-dicarboximide) ethyl acrylate, EM212 cyclotrimethylolpropane formal acrylate CTFA, EM 2102-phenoxyethyl acrylate PHEA, EM70 isobornyl acrylate IBOA, EM71-E cyclohexyl methacrylate CHMA, EM222 dipropylene glycol diacrylate DPGDA, EM22031, 9-nonanediol diacrylate NDDA.
Preferably, the auxiliary agent comprises a leveling agent and an antifoaming agent, and the mass ratio of the leveling agent to the antifoaming agent is 1-3: 1.
further, the leveling agent is one of polydimethylsiloxane, polymethylphenylsiloxane and organic silicon modified polysiloxane.
Further, the defoaming agent is a polyether modified organic silicon defoaming agent.
In the invention, the reaction process of preparing the phosphorus-containing acrylate prepolymer by using the 2-methyl-2, 5-dioxo-1, 2-oxaphospholane OP and the hydroxyl acrylate compound comprises the following steps:
wherein, the general formula of the hydroxyl acrylic ester compound is
R1＝H2C ═ CH-or
R2＝——CH2-CH2——、or-CH2-CH2-CH2-CH2-one of the above.
The invention has the beneficial effects that:
1. the prepolymer which is prepared into the photosensitive resin has good flame retardant property by using the phosphorus-containing acrylate prepolymer containing the flame retardant group.
2. The prepolymer has a flame-retardant structure, and after the prepolymer is matched with polyurethane acrylate, a catalyst and an auxiliary agent to form photosensitive resin, the photosensitive resin can not form substances which pollute the environment or are harmful to the health of people in the curing or later use process, so that the prepolymer is safe and environment-friendly, and avoids the environmental threat and the harm to the health of people when bromine-containing flame retardant or antimony pentoxide-containing inorganic substances are added for the flame retardance of the photosensitive resin.
3. The phosphorus-containing acrylate prepolymer has both oil-soluble ester structure and water-soluble hydroxyl structure, so that the prepolymer can be used for both oil-soluble and water-soluble photosensitive resin systems.
4. The prepared photosensitive resin has the advantages of low viscosity, high curing speed, small shrinkage, good flame retardant property, safety and environmental protection.
Drawings
FIG. 1 is an FTIR spectrum of a phosphorus-containing hydroxyethyl acrylate prepolymer
FIG. 2 is NMR-H of phosphorus-containing hydroxyethyl acrylate prepolymer1Atlas
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
13.40g (0.1mol) of OP and 11.60g (0.1mol) of hydroxyethyl acrylate are put into a three-neck flask, and 2.00g of catalyst strong-acid cation exchange resin PK208LH (the mass of the catalyst is 8 percent of the mass sum of OP and hydroxyethyl acrylate) and 0.0250g of polymerization inhibitor hydroquinone (the mass of the polymerization inhibitor is 0.1 percent of the mass sum of OP and hydroxyethyl acrylate) are added, and the reaction is stopped after 5 hours of reaction at 110 ℃. And (3) separating the product phosphorus-containing acrylate prepolymer in the system: adding 100mL of ethyl acetate, continuing stirring for 30min, after the temperature of the system is reduced to room temperature, separating PK208LH cationic resin from the reaction liquid by cloth funnel filtration (soaking the separated PK208LH resin in ethanol to remove phosphorus-containing acrylate prepolymer for recycling), adding the filtrate into a 250mL pear-shaped funnel, adding 50mL saturated saline solution two phases, violently mixing to remove the polymerization inhibitor and unreacted OP, discharging the lower layer with the saturated saline solution layer having a higher specific gravity, and continuously washing the saturated saline solution three times by 50mL each time. The lower layer was combined with brine and extracted twice with 200mL of ethyl acetate, and the ethyl acetate phase extract was combined with the oil phase obtained in the upper layer and dried over anhydrous sodium sulfate, followed by distillation under reduced pressure to remove ethyl acetate and hydroxyethyl acrylate to obtain 18g of a phosphorus-containing acrylate prepolymer in a molar yield of 72%.
61.33g of phosphorus-containing acrylate prepolymer prepared by the method, 617026.67g of aliphatic polyurethane acrylate, 5g of cyclotrimethylolpropane methylal acrylate as an active diluent EM212, 11735g of free radical photoinitiator and 2g of auxiliary agent (consisting of 1g of polydimethylsiloxane leveling agent and 1g of polyether modified organic silicon defoaming agent) are mixed and stirred uniformly to obtain the flame-retardant SLA photosensitive resin. The polyether modified organic silicon defoaming agent is a ZK-203 organic silicon defoaming agent produced by Tianjin Zhongke chemical industry Co.
Example 2
13.40g (0.1mol) of OP and 13.00g (0.1mol) of acrylic acid-beta-hydroxypropyl are taken to be put into a three-neck flask, 2.00g of catalyst strong acid cation exchange resin PK208LH (the mass of the catalyst is 7.58 percent of the mass sum of the OP and the acrylic acid-beta-hydroxypropyl) and 0.0264g of polymerization inhibitor hydroquinone (the mass of the polymerization inhibitor is 0.1 percent of the mass sum of the OP and the acrylic acid-beta-hydroxypropyl) are added to react for 5 hours at 110 ℃ to obtain a phosphorus-containing acrylic ester prepolymer (the separation method is the same as that in example 1), and the molar yield is 68 percent.
63.33g of the prepared phosphorus-containing acrylate prepolymer, 617021.67g of aliphatic polyurethane acrylate, 10g of active diluent EM 2102-phenoxyethyl acrylate, 11733g of free radical photoinitiator and 2g of auxiliary agent (consisting of 1g of polydimethylsiloxane leveling agent and 1g of polyether modified organic silicon defoamer) are mixed and stirred uniformly to obtain the flame-retardant SLA photosensitive resin.
Example 3
13.40g (0.1mol) of OP and 14.40g (0.1mol) of 4-hydroxybutyl acrylate are put into a three-neck flask, and 2.00g of catalyst strong acid cation exchange resin PK208LH (the mass of the catalyst is 7.18 percent of the mass sum of OP and 4-hydroxybutyl acrylate) and 0.0278g of polymerization inhibitor hydroquinone (the mass of the polymerization inhibitor is 0.1 percent of the mass sum of OP and 4-hydroxybutyl acrylate) are added into the three-neck flask to react for 5 hours at 110 ℃ to obtain a phosphorus-containing acrylate prepolymer (the separation method is the same as in example 1), and the molar yield is 79 percent.
40g of the prepared phosphorus-containing acrylate prepolymer, 617043g of aliphatic polyurethane acrylate, 15g of active diluent EM70 isobornyl acrylate, 11731g of free radical photoinitiator and 1g of auxiliary agent (consisting of 0.5g of polydimethylsiloxane leveling agent and 0.5g of polyether modified organic silicon defoamer) are mixed and stirred uniformly to obtain the flame-retardant SLA photosensitive resin.
Example 4
13.40g (0.1mol) of OP and 13g (0.1mol) of hydroxyethyl methacrylate were put into a three-necked flask, and 2.11g of a catalyst strongly acidic cation exchange resin PK212LH (the mass of the catalyst was 8% of the mass of the sum of OP and hydroxyethyl methacrylate) and 0.132g of a polymerization inhibitor p-hydroxyanisole (the mass of the polymerization inhibitor was 0.5% of the mass of the sum of OP and hydroxyethyl methacrylate) were added to react at 110 ℃ for 5 hours to obtain a phosphorus-containing acrylate prepolymer (the separation method was the same as in example 1), with a molar yield of 65%.
15g of the prepared phosphorus-containing acrylate prepolymer, 10073g of aromatic polyurethane acrylate 6146-95 g, 7g of active diluent EM222 dipropylene glycol diacrylate, 9074.5g of free radical photoinitiator and 0.5g of auxiliary agent (consisting of 0.25g of flatting agent polymethylphenylsiloxane and 0.25g of polyether modified organic silicon defoamer) are mixed and stirred uniformly to obtain the flame-retardant SLA photosensitive resin.
Example 5
13.40g (0.1mol) of OP and 14.40g (0.1mol) of beta-hydroxypropyl methacrylate are put into a three-neck flask, and 1.39g of catalyst strong acid cation exchange resin PK212LH (the mass of the catalyst is 5 percent of the mass sum of OP and beta-hydroxypropyl methacrylate) and 0.278g of polymerization inhibitor p-benzoquinone (the mass of the polymerization inhibitor is 1 percent of the mass sum of OP and beta-hydroxypropyl methacrylate) are added to react for 6 hours at 120 ℃ to obtain a phosphorus-containing acrylate prepolymer (the separation method is the same as that of example 1), and the molar yield is 70 percent.
50g of the prepared phosphorus-containing acrylate prepolymer, 620234.5g of epoxy acrylate, 12g of reactive diluent (consisting of 6gEM212 g of cyclotrimethylolpropane methylal acrylate and 6gEM 2102-phenoxyethyl acrylate), 3692g of free radical photoinitiator and 1.5g of auxiliary agent (consisting of 1g of flatting agent polymethylphenylsiloxane and 0.5g of polyether modified organic silicon defoamer), and uniformly mixing and stirring to obtain the flame-retardant SLA photosensitive resin.
Example 6
13.40g (0.1mol) of OP and 11.6g (0.1mol) of hydroxyethyl acrylate are put into a three-neck flask, 1.5g of catalyst strong acid cation exchange resin RCP106M (the mass of the catalyst is 6 percent of the mass sum of OP and hydroxyethyl acrylate) and 0.5g of polymerization inhibitor N-phenyl-2-naphthylamine (the mass of the polymerization inhibitor is 2 percent of the mass sum of OP and hydroxyethyl acrylate) are added, and the mixture is reacted for 5.5h at 120 ℃ to obtain a phosphorus-containing acrylate prepolymer (the separation method is the same as in example 1), wherein the molar yield is 75 percent.
75g of the prepared phosphorus-containing acrylate prepolymer, 631515.5g of polyester acrylate, 5g of active diluent EM 2102-phenoxyethyl acrylate, 1843g of free radical photoinitiator and 1.5g of auxiliary agent (consisting of 1g of leveling agent organic silicon modified polysiloxane and 0.5g of polyether modified organic silicon defoaming agent) are mixed and stirred uniformly to obtain the flame-retardant SLA photosensitive resin.
Example 7
13.40g (0.1mol) of OP and 13g (0.1mol) of beta-hydroxypropyl acrylate are taken to be put into a three-neck flask, 1.85g of catalyst strong acid cation exchange resin D001 (the mass of the catalyst is 7 percent of the mass sum of the OP and the beta-hydroxypropyl acrylate) and 1.32g of polymerization inhibitor p-tert-butylcatechol (the mass of the polymerization inhibitor is 5 percent of the mass sum of the OP and the beta-hydroxypropyl acrylate) are added, and the mixture is reacted for 5.5 hours at 110 ℃ to obtain a phosphorus-containing acrylate prepolymer (the separation method is the same as the example 1), wherein the molar yield is 78 percent.
63.6g of the prepared phosphorus-containing acrylate prepolymer, 632015g of polyester acrylate, 15g of reactive diluent (consisting of 5gEM70 isobornyl acrylate and 10gEM222 dipropylene glycol diacrylate), 6515g of free radical photoinitiator and 1.4g of auxiliary agent (consisting of 0.7g of leveling agent organic silicon modified polysiloxane and 0.7g of polyether modified organic silicon defoamer) are mixed and stirred uniformly to obtain the flame-retardant SLA photosensitive resin.
Example 8
13.40g (0.1mol) of OP and 14.4g (0.1mol) of 4-hydroxybutyl acrylate were taken in a three-necked flask, and 2.22g of a catalyst, a strong acid cation exchange resin D001 (the mass of the catalyst is 8% of the mass sum of OP and 4-hydroxybutyl acrylate) and 1.112g of a polymerization inhibitor, p-hydroxyanisole (the mass of the polymerization inhibitor is 4% of the mass sum of OP and 4-hydroxybutyl acrylate) were added, and the mixture was reacted at 120 ℃ for 6 hours to obtain a phosphorus-containing acrylate prepolymer (the separation method was the same as in example 1), with a molar yield of 80%.
35.2g of the prepared phosphorus-containing acrylate prepolymer, 50g of acrylate (consisting of 25g of aliphatic polyurethane acrylate 6170 and 25g of epoxy acrylate 6202), 10g of isobornyl acrylate serving as an active diluent EM70, 8193g of a free radical photoinitiator and 1.8g of an auxiliary agent (consisting of 1g of flatting agent organic silicon modified polysiloxane and 0.8g of polyether modified organic silicon defoaming agent) are mixed and stirred uniformly to obtain the flame-retardant SLA photosensitive resin.
Example 9
13.40g (0.1mol) of OP and 13g (0.1mol) of hydroxyethyl methacrylate are put into a three-neck flask, 1.45g of catalyst (the mass of the catalyst is 5.5 percent of the mass sum of OP and hydroxyethyl methacrylate) is added, the catalyst consists of strongly acidic cation exchange resin PK212LH and NKC-9 according to the mass ratio of 1:1, 0.66g of polymerization inhibitor (the mass of the polymerization inhibitor is 2.5 percent of the mass sum of OP and hydroxyethyl methacrylate) is added, the polymerization inhibitor consists of p-benzoquinone and N-phenyl-2-naphthylamine according to the mass ratio of 1:1, and the mixture is reacted for 5 hours at the temperature of 130 ℃ to obtain a phosphorus-containing acrylate prepolymer (the separation method is the same as in example 1), and the molar yield is 74 percent.
16.4g of the prepared phosphorus-containing acrylate prepolymer, 75g of acrylate (consisting of 25g of aliphatic urethane acrylate 6170 and 50g of polyester acrylate 6315), 6g of active diluent EM222 dipropylene glycol diacrylate, 1.6g of free radical photoinitiator ITX1g and 1.6g of auxiliary agent (consisting of 1.2g of flatting agent polydimethylsiloxane and 0.4g of polyether modified organic silicon defoamer) are mixed and stirred uniformly to obtain the flame-retardant SLA photosensitive resin.
Example 10
13.40g (0.1mol) of OP and 14.4g (0.1mol) of beta-hydroxypropyl methacrylate are put into a three-neck flask, and 1.81g of catalyst (the mass of the catalyst is 6.5 percent of the sum of the mass of OP and the mass of the beta-hydroxypropyl methacrylate) is added, wherein the catalyst is prepared by mixing strongly acidic cation exchange resins PK212LH, RCP106M, D001 and NKC-9 according to the mass ratio of 1: 1:1, adding 1.39g of polymerization inhibitor (the mass of the polymerization inhibitor is 5 percent of the sum of the mass of OP and beta-hydroxypropyl methacrylate), and adding the polymerization inhibitor which is benzenediol, p-benzoquinone and p-hydroxyanisole according to the mass ratio of 1:1, at 130 ℃ for 5h to obtain a prepolymer of phosphorus-containing acrylate (the isolation procedure is the same as in example 1), with a molar yield of 69%.
20.2g of the prepared phosphorus-containing acrylate prepolymer, 60g of acrylate (consisting of 30g of epoxy acrylate 6202 and 30g of polyester acrylate 6315), 14g of reactive diluent (consisting of 4gEM70 isobornyl acrylate, 5gEM212 cyclotrimethylolpropane methylal acrylate and 5gEM 2102-phenoxyethyl acrylate), 5g of free radical photoinitiator (consisting of 11732.5g and 9072.5 g), 0.8g of auxiliary agent (consisting of 0.4g of leveling agent organosilicon modified polysiloxane and 0.4g of polyether modified organosilicon defoamer), and uniformly mixing and stirring to obtain the flame-retardant photosensitive resin.
And (3) performance testing:
the IR spectra of the phosphorus-containing hydroxyethyl acrylate prepolymer, hydroxyethyl acrylate and OP obtained in example 1 are shown in FIG. 1, and the phosphorus-containing hydroxyethyl acrylate prepolymer obtained in example 11The H-NMR (DMSO-D6) spectrum is shown in FIG. 2.
From the curve b in the infrared spectrum of FIG. 1, it can be seen that the distance between the probe and the probe is 1709cm-1The vibration is C ═ O stretching vibration at 1637cm-1A characteristic absorption peak of C ═ C at1130cm-1Characteristic absorption peak of P ═ O at 979cm-1The C-P stretching vibration absorption peak is corresponded to, and the existence of acrylic acid groups and characteristic groups of phosphorus in target molecules is indicated. In addition, when the spectrum b is compared with the spectra a and C, the characteristic absorption peaks of C-O, C-C, P-O, C-P and the like are all red shifted, which indicates that the hydroxyethyl acrylate and the OP react. From FIG. 21H-NMR (DMSO-D6) pattern analysis results: 1.28-1.44(3H, -CH)/ppm3，a)，1.76-2.43(4H，-CH2-，c,d)，3.59-4.29(4H，-CH2-，e,f)，5.93-6.39(3H，-CH＝CH2G, h, i). From FT-IR analysis and1H-NMR analysis can prove that the synthesized product is phosphorus-containing hydroxyethyl acrylate.
The SLA photosensitive resins obtained in examples 1-10 were subjected to performance testing, the results of which are shown in the following table:
as can be seen from the above table, the SLA photosensitive resins obtained in examples 1-10 have excellent flame retardant performance under the condition that the curing time, gel fraction, viscosity and volume shrinkage rate are all kept good.
Claims (10)
1. The flame-retardant SLA photosensitive resin for 3D printing is characterized by comprising the following components in percentage by weight: 15-75% of phosphorus-containing acrylate prepolymer, 15-75% of acrylate, 1-5% of free radical initiator, 0.5-2% of auxiliary agent and 5-15% of reactive diluent, wherein the sum of the weight percentages of the components is 100%; the structural general formula of the phosphorus-containing acrylate prepolymer is
Wherein,
R1＝H2c is CH-or
R2＝-CH2-CH2-、or-CH2-CH2-CH2-CH2-one of the above.
2. The photosensitive resin as claimed in claim 1, wherein the phosphorus-containing acrylate prepolymer is obtained by mixing 2-methyl-2, 5-dioxo-1, 2-oxyphospholane OP and a hydroxyl acrylate compound in a molar ratio of 1:1, adding a catalyst and a polymerization inhibitor, and reacting at 110-130 ℃ for 5-6 h;
the hydroxyl acrylic ester compound is one of hydroxyethyl acrylate, beta-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, hydroxyethyl methacrylate and beta-hydroxypropyl methacrylate.
3. The photosensitive resin according to claim 2, wherein the polymerization inhibitor is one or more of hydroquinone, p-hydroxyanisole, p-benzoquinone, N-phenyl-2-naphthylamine, p-tert-butylcatechol, and the amount of the polymerization inhibitor is 0.1-5.0% of the sum of the amounts of the 2-methyl-2, 5-dioxo-1, 2-oxyphospholane OP and the hydroxyacrylate compound.
4. The photosensitive resin of claim 2, wherein the catalyst is one or more of strong acid cation exchange resins PK208LH, PK212LH, RCP106M, D001 and NKC-9, and the amount of the catalyst is 5-8% of the sum of the amounts of the 2-methyl-2, 5-dioxo-1, 2-oxaphospholane OP and the hydroxyacrylate compound.
5. The photosensitive resin of claim 1, wherein the acrylate is one or more of aliphatic urethane acrylate, aromatic urethane acrylate, epoxy acrylate or polyester acrylate.
6. The photosensitive resin of claim 1, wherein the radical initiator is one or more of the photoinitiators 1173, 184, 907, 369, 651, 819 and ITX.
7. The photosensitive resin of claim 1, wherein the reactive diluent is one or more selected from the group consisting of functional acrylate monomers consisting of 2- (1, 2-cyclohexane-1, 2-dicarboxyiimide) ethyl acrylate, cyclic trimethylolpropane formal acrylate, 2-phenoxyethyl acrylate, isobornyl acrylate, cyclohexyl methacrylate, dipropylene glycol diacrylate, and 1, 9-nonanediol diacrylate.
8. The photosensitive resin according to claim 1, wherein the auxiliary agent comprises a leveling agent and an antifoaming agent, and the mass ratio of the leveling agent to the antifoaming agent is 1-3: 1.
9. the photosensitive resin according to claim 8, wherein the leveling agent is one of polydimethylsiloxane, polymethylphenylsiloxane, and silicone-modified polysiloxane.
10. The photosensitive resin according to claim 8, wherein the defoaming agent is a polyether modified silicone defoaming agent.
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| CN108587100A (en) * | 2018-05-18 | 2018-09-28 | 深圳永昌和科技有限公司 | Environment and human body friendly vegetable oil base ultraviolet light cure 3D printing resin |
| CN108727550A (en) * | 2018-04-23 | 2018-11-02 | 浙江锐胜新材料有限公司 | A kind of photosensitive resin and its application |
| CN111154211A (en) * | 2019-12-26 | 2020-05-15 | 诺思贝瑞新材料科技（苏州）有限公司 | Photocuring composition for 3D printing and photocuring part |
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| CN106814537A (en) * | 2015-11-30 | 2017-06-09 | 乐凯华光印刷科技有限公司 | A kind of light sensitive imaging composition comprising hexamethylene acid amides monofunctional acrylate copolymer |
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