CN109867760A - A kind of 3D printing cashew nut phenolic group photosensitive resin and preparation method thereof - Google Patents
A kind of 3D printing cashew nut phenolic group photosensitive resin and preparation method thereof Download PDFInfo
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- CN109867760A CN109867760A CN201910101029.1A CN201910101029A CN109867760A CN 109867760 A CN109867760 A CN 109867760A CN 201910101029 A CN201910101029 A CN 201910101029A CN 109867760 A CN109867760 A CN 109867760A
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- cashew nut
- printing
- phenolic group
- photosensitive resin
- nut phenolic
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- 244000226021 Anacardium occidentale Species 0.000 title claims abstract description 91
- 235000020226 cashew nut Nutrition 0.000 title claims abstract description 91
- 239000011347 resin Substances 0.000 title claims abstract description 64
- 229920005989 resin Polymers 0.000 title claims abstract description 64
- 238000010146 3D printing Methods 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims description 53
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Substances O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 55
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 12
- 239000003112 inhibitor Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 3
- SLGWESQGEUXWJQ-UHFFFAOYSA-N formaldehyde;phenol Chemical compound O=C.OC1=CC=CC=C1 SLGWESQGEUXWJQ-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000000016 photochemical curing Methods 0.000 claims description 22
- 239000007859 condensation product Substances 0.000 claims description 18
- 238000005516 engineering process Methods 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 229920000642 polymer Polymers 0.000 claims description 13
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 12
- 238000001723 curing Methods 0.000 claims description 12
- 238000011282 treatment Methods 0.000 claims description 11
- 238000010792 warming Methods 0.000 claims description 11
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- -1 hexa-methylene four Amine Chemical compound 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 238000007639 printing Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 235000013399 edible fruits Nutrition 0.000 claims description 3
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- 230000008021 deposition Effects 0.000 claims description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims 2
- WRLRISOTNFYPMU-UHFFFAOYSA-N [S].CC1=CC=CC=C1 Chemical compound [S].CC1=CC=CC=C1 WRLRISOTNFYPMU-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims 1
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 abstract description 5
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 abstract description 5
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 abstract description 5
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 abstract description 5
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 4
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 abstract description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 abstract 2
- 239000008096 xylene Substances 0.000 abstract 2
- 238000001704 evaporation Methods 0.000 abstract 1
- 239000004312 hexamethylene tetramine Substances 0.000 abstract 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 abstract 1
- 235000014571 nuts Nutrition 0.000 abstract 1
- 239000005011 phenolic resin Substances 0.000 description 15
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 8
- 238000011161 development Methods 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 239000000853 adhesive Substances 0.000 description 5
- 230000001070 adhesive effect Effects 0.000 description 5
- 238000005452 bending Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000005028 tinplate Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000007711 solidification Methods 0.000 description 4
- 230000008023 solidification Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- XVZXOLOFWKSDSR-UHFFFAOYSA-N Cc1cc(C)c([C]=O)c(C)c1 Chemical group Cc1cc(C)c([C]=O)c(C)c1 XVZXOLOFWKSDSR-UHFFFAOYSA-N 0.000 description 1
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- ZMDDERVSCYEKPQ-UHFFFAOYSA-N Ethyl (mesitylcarbonyl)phenylphosphinate Chemical compound C=1C=CC=CC=1P(=O)(OCC)C(=O)C1=C(C)C=C(C)C=C1C ZMDDERVSCYEKPQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 210000001624 hip Anatomy 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002365 multiple layer Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 1
Landscapes
- Materials For Photolithography (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
本发明公开了一种3D打印用腰果酚基光敏树脂及其制备方法，其制备方法为以腰果酚和六亚甲基四胺为原料进行混合，然后加入二甲苯作为溶剂混合后，制得腰果酚甲醛缩聚物；再以甲苯磺酸为催化剂，1，4‑对苯二酚为阻聚剂，二甲苯为溶剂，将其加入到腰果酚甲醛缩聚物和带光敏基团类单体的混合物中，制得腰果酚基光固化预聚体；然后将溶剂蒸发后，将腰果酚基光固化预聚体和光引发剂按质量比为100：0.1～10的比例混合，并充分搅拌后，即可得到3D打印用腰果酚基光敏树脂，本发明方案固化和交联可控、固化时间短且实施可靠。The invention discloses a cardanol-based photosensitive resin for 3D printing and a preparation method thereof. The preparation method comprises the following steps: mixing cardanol and hexamethylenetetramine as raw materials, then adding xylene as a solvent and mixing to prepare cashew nuts Phenol-formaldehyde polycondensate; then use toluenesulfonic acid as a catalyst, 1,4-hydroquinone as a polymerization inhibitor, and xylene as a solvent, and add it to the mixture of cardanol-formaldehyde polycondensate and monomers with photosensitive groups Then, after evaporating the solvent, the cardanol-based photocurable prepolymer and the photoinitiator are mixed in a mass ratio of 100:0.1 to 10, and fully stirred, that is, The cardanol-based photosensitive resin for 3D printing can be obtained, and the solution of the present invention has controllable curing and cross-linking, short curing time and reliable implementation.
Description
Technical field
The present invention relates to photosensitive resin field, especially a kind of 3D printing cashew nut phenolic group photosensitive resin and its preparation side
Method.
Background technique
The three-dimensional fast shaping technology development in recent years of 3D printing (Three Dimensional Printing) is made us looking steadily
Mesh.It manufactures product with materials such as metal, ceramics, polymer, by multiple-layer stacked printing type.Currently, three-dimensional fast rapid-result
The use of type technology has involved the multiple fields such as industry, medical treatment, cultural creative, has a extensive future.3D printing industry has become
Numerous research staff, allocation of funds hot fields.Photocuring 3D printing forming technique is the hot spot studied at present, and core is asked
One of topic is the exploitation of photosensitive resin.Photocuring system generally by oligomer, reactive diluent and photoinitiator and all kinds of adds
Agent is added to form.For the ultraviolet photosensitive resin of moulding material free radical type used in photocuring, mainly with acrylate and polyurethane
Acrylate is as prepolymer, and for most of performed polymer all using petroleum chemicals as primary raw material, these products are big in consumption in the market
Harm inevitably is brought to environment and human body while measuring petroleum resources.It is opened with renewable resource substitution fossil resources development
It is one of development priority direction of industry that substance light-cured resin, which occurs, and meets the requirement of greenization sustainable development, is had become
For the development trend of a certainty.
Anacardol (Cardanol) is the main component of cashew nut shell liquid (Cashew Nut Shell Liquid), cashew nut shell
Liquid is a kind of thick liquid russet, extract in the shell of the fruit for the cashew nut tree planted from the torrid zone or subtropical zone, is
The by-product of cashew nut in process, not only abundance, and also price is very cheap, is a kind of reproducible natural green
Resource.Not only contain phenolic hydroxyl group in anacardol molecular structure, side chain also contains unsaturated alkyl long-chain, can under ultraviolet excitation
Carry out photocuring polymerization reaction, it has also become coating, hot spot Material Field research and paid close attention to.In recent years, related anacardol light is solid
The report for changing research gradually increases, be mainly esterified including anacardol direct ultraviolet photocuring, acroleic acid esterification, epoxy acrylic,
Vinylated, phenolic resin, isocyanates graft modification and the research such as composite, nano-compound modified.And these waists
It is reactivity site that fruit phenol photo-curing material, which mainly utilizes anacardol monomer phenolic hydroxyl group and side chain unsaturated double-bond, passes through etherificate
Or methacryloxy or acryloxy are introduced into molecular structure and prepare photo-curing monomer and oligomer by esterification,
But uv power is high when often solidifying, and curing time is long, limits the further utilization of cashew nut phenolic group photocuring.
Therefore research and development can direct 3D printing cashew nut phenol resin, meet the requirement of greenization sustainable development, while can be with
Reduce the cost of 3D photocuring photosensitive resin.
And it carries out 3D printing solidification after being modified using the formaldehyde condensation products of anacardol not report so far.
Summary of the invention
The case where for the prior art and a kind of insufficient, controllable, solidification that the purpose of the present invention is to provide solidifications and crosslinking
Time is short and implements reliable 3D printing cashew nut phenolic group photosensitive resin and preparation method thereof.
In order to realize above-mentioned technical purpose, the technical solution adopted by the present invention are as follows:
A kind of preparation method of 3D printing cashew nut phenolic group photosensitive resin, using anacardol and hexa as raw material into
Anacardol formaldehyde condensation products are made after dimethylbenzene is then added as solvent mixing in row mixing；It is again catalysis with toluenesulfonic acid
Agent, Isosorbide-5-Nitrae-hydroquinone are polymerization inhibitor, and dimethylbenzene is solvent, adds it to anacardol formaldehyde condensation products and with photosensitive group class
In the mixture of monomer, cashew nut phenolic group photocuring performed polymer is made；Then after solvent being evaporated, by cashew nut phenolic group photocuring pre-polymerization
Body and photoinitiator are the ratio mixing of 100:0.1~10 in mass ratio, and after being sufficiently stirred, 3D printing cashew nut can be obtained
Phenolic group photosensitive resin.
Further, the anacardol derives from cashew nut shell liquid.
Preferably, specifically comprise the following steps:
(1) using dimethylbenzene as solvent, 100 parts of cashew nut shell liquids and 4 parts of hexas is added thereto, are then added
Distilled water, enable its 80~90 DEG C hybrid reaction 1~3 hour, then heat to 130~140 DEG C of reflow treatments 1~2 hour, make
Obtain anacardol formaldehyde condensation products；
(2) 0.8 part of p-methyl benzenesulfonic acid is taken to make as catalyst, 1 part of Isosorbide-5-Nitrae-hydroquinone as polymerization inhibitor, 30 parts of dimethylbenzene
It for solvent, is mixed, then adds anacardol formaldehyde condensation products made from 25~50 parts of steps (2) and 50~75 parts of band light
Quick base class monomer is mixed, and reflow treatment 6h under the conditions of 80~90 DEG C, then is warming up to 100~110 DEG C and continue instead
It answers 5~6 hours, cashew nut phenolic group photocuring performed polymer is made；
(3) by after the solvent rotary evaporation in cashew nut phenolic group photocuring performed polymer made from step (2), then it is drawn with light
Hair agent is that the ratio of 100:0.1~10 is thoroughly mixed in mass ratio, can be prepared by 3D printing cashew nut phenolic group photosensitive resin.
It preferably, is acrylic acid, methacrylic acid, acryloyl chloride, methyl with photosensitive base class monomer described in step (2)
One of glycidyl acrylate.
Preferably, photoinitiator described in step (3) includes 2- hydroxy-2-methyl -1- phenylacetone, 1- hydroxy cyclohexylphenyl
Base phenyl ketone, 2- methyl -2- (4- morpholinyl) -1- [4- (methyl mercapto) phenyl] -1- acetone, 2,4,6- trimethylbenzoyl
One of base-diphenyl phosphine oxide, 2,4,6- trimethylbenzoyl phenyl phosphinic acid ethyl ester.
Preferably, the viscosity of cashew nut phenolic group photocuring performed polymer obtained is 1132~1711mPas in step (2).
Preferably, in step (3) 3D printing obtained with cashew nut phenolic group photosensitive resin ultraviolet light wave a length of 365~
405nm, uv power are 100~133mW/cm2Under conditions of lighting process the ultra-violet curing time be 1~100s.
The 3D printing application of cashew nut phenolic group photosensitive resin obtained by a kind of preparation method according to, is loaded
3D printing product is carried out in 3D printing equipment.
Further, photocuring three-dimensional printing technology used by the 3D printing equipment be stereolithography apparatus technology,
One of digital light projection technology, Laser Clad Deposition technology.
3 D-printing cashew nut phenol resin anacardol and formaldehyde are initially formed condensation polymer, can regulate and control cashew nut phenol resin at
Type shrinking percentage, bending property etc..It is double that carbon carbon in cashew nut phenol resin is regulated and controled by the control with photosensitive group class monomer dosage simultaneously
The content of key (C=C) is solidified with the ultraviolet light radical crosslinking of this controllable adjustment cashew nut phenol resin, and then regulates and controls 3 D-printing
Performance, this 3D printing are applicable to a variety of three-dimensional Stereolithography technologies with cashew nut phenol resin.
Part reaction equation involved in this programme is as follows:
By using above-mentioned technical solution, compared with prior art, the present invention it, which has the beneficial effect that, passes through this
3D printing cashew nut phenolic group photosensitive resin obtained by scheme of the invention can be under 355~405nm ultraviolet light irradiation, by with photosensitive
Group class monomer dosage changes the content of carbon-carbon double bond in resin (C=C), i.e. control free-radical contents realize anacardol tree
The controllable UV optical free radical cross-linked polymeric of rouge.Also, test indicate that cashew nut phenol resin cross-linked speed realizes promotion and can
Control, i.e. ultra-violet curing time can be promoted by 600s and foreshorten to 10-180s, and in addition the 3D printing cashew nut phenolic group photosensitive resin can lead to
Control strip photosensitive group class monomer dosage is crossed to regulate and control the service performance of cashew nut phenol resin, including glossiness, flexibility, attachment
Power, hardness, shock resistance；It is the glossiness of anacardol photosensitive resin, flexible with the increase of photosensitive group class content of monomer
Property, adhesive force, hardness, impact strength all make moderate progress.Furthermore the 3D printing cashew nut phenolic group photosensitive resin has anacardol
Excellent properties of resin such as thermo oxidative stability, electrical insulation capability, weatherability etc.；The ultraviolet light fast solidification of cashew nut phenol resin,
It is set to have the potential application ability in lacquer craftwork automatic technology and increases material manufacturing technology field；Meanwhile passing through photosensitive base
The regulation of group's class type and dosage can not only finely tune resin service performance and the polymerization of ultraviolet light radical crosslinking, can also reduce
The application cost of cashew nut phenol resin.
Specific embodiment
Embodiment 1
A kind of preparation method of 3D printing cashew nut phenolic group photosensitive resin comprising following steps:
1) it using dimethylbenzene as solvent, is added 100g cashew nut shell liquid (CNSL), 4g hexa (H powder), then adds again
Enter a certain amount of distilled water, react mixed system at 80~90 DEG C 1~3 hour, is then warming up to 130~140 DEG C again and returns
It stream process 1~2 hour, is made anacardol formaldehyde condensation products (PCF)；
2) using 0.8g p-methyl benzenesulfonic acid as catalyst, 1g Isosorbide-5-Nitrae-hydroquinone is polymerization inhibitor, and 30g dimethylbenzene is solvent, into
After row mixing, 50g anacardol formaldehyde condensation products (PCF) and 50g acryloyl chloride (AC) is added, then in 80~90 DEG C of temperature conditions
Lower reflow treatment 6 hours is then warming up to 100~110 DEG C, react 5~6 hours again obtaining acryloyl chloride cashew pnenolic aldehyde
Photosensitive resin (MPCF), i.e. cashew nut phenolic group photocuring performed polymer；Wherein, the viscosity of acryloyl chloride cashew pnenolic aldehyde photosensitive resin is
1132mPa·s；
3) by after the solvent rotary evaporation in cashew nut phenolic group photocuring performed polymer made from step (2), by 50g acryloyl chloride
Cashew pnenolic aldehyde photosensitive resin is added in the photoinitiator 1- hydroxycyclohexyl phenyl ketone (184) of its mass ratio 3% sufficiently
Stirring, obtains 3D printing cashew nut phenolic group photosensitive resin.
Performance test
3D printing obtained is spread evenly across in clean tinplate sheet with cashew nut phenolic group photosensitive resin (with a thickness of 100 μ
M), then it is put into 365nm ultraviolet light (100mW/cm2) irradiate treatment with irradiation in lower ultra-violet curing case, wherein 3D printing cashew nut
The cure times of phenolic group photosensitive resin are 40s, and film completion of cure, surface is smooth.Resin film bending property 2mm is not split
Trace, hardness 4B, adhesive force are 2 grades, and the impact resistance of cured film reaches 60kgcm.It is printed with the SLA printer of Form2
At batten, the molding shrinkage of batten is 0.3%.
Embodiment 2
1) it using dimethylbenzene as solvent, is added 100g cashew nut shell liquid (CNSL), 4g hexa (H powder), then adds again
Enter a certain amount of distilled water；It reacts mixed system at 80~90 DEG C 1~3 hour, is then warming up to 130~140 DEG C again and returns
It stream process 1~2 hour, is made anacardol formaldehyde condensation products (PCF)；
2) using 0.8g p-methyl benzenesulfonic acid as catalyst, 1g Isosorbide-5-Nitrae-hydroquinone is polymerization inhibitor, and 30g dimethylbenzene is solvent, into
After row mixing, 34g anacardol formaldehyde condensation products (PCF) and 66g methacrylic acid (MAA) is added, 80~90 DEG C of temperature next time
Stream process 6 hours, it is then warming up to 100~110 DEG C again, carries out obtaining methacrylic acid cashew pnenolic aldehyde in reaction 5~6 hours photosensitive
Resin, viscosity 1352mPas；
3) by after the solvent rotary evaporation in methacrylic acid cashew pnenolic aldehyde photosensitive resin made from step (2), by 50g first
Base acrylic acid cashew pnenolic aldehyde photosensitive resin is added to the 2,4,6- trimethylbenzoyl-of the photoinitiator of its mass ratio 3%
Mixing in diphenyl phosphine oxide (TPO), and be sufficiently stirred, obtain 3D printing cashew nut phenolic group photosensitive resin.
Performance test
3D printing obtained is spread evenly across in clean tinplate sheet with cashew nut phenolic group photosensitive resin (with a thickness of 100 μ
M), then it is put into 365nm ultraviolet light (100mW/cm2) irradiate treatment with irradiation in lower ultra-violet curing case.3D printing cashew nut phenolic group
The cure times of photosensitive resin are 15s, and film completion of cure, surface is smooth.Resin film bending property 2mm does not occur slight crack,
Hardness 3B, 2 grades of adhesive force, the impact resistance of cured film reaches 75kgcm.It is printed as with the SLA 3D printer of Forms2
Batten, the molding shrinkage of batten are 0.2%.
Embodiment 3
1) it using dimethylbenzene as solvent, is added 100g cashew nut shell liquid (CNSL), 4g hexa (H powder) is then added
A certain amount of distilled water reacts mixed system at 80~90 DEG C 1~3 hour, is then warming up to 130~140 DEG C of reflux again
Processing 1~2 hour, obtains anacardol formaldehyde condensation products (PCF)；
2) using 0.8g p-methyl benzenesulfonic acid as catalyst, 1g Isosorbide-5-Nitrae-hydroquinone is polymerization inhibitor, and 30g dimethylbenzene is solvent, into
After row mixing, 50g anacardol formaldehyde condensation products (PCF) and 50g acrylic acid (AA) is added, is flowed next time in 80~90 DEG C of temperature conditions
Processing 6 hours, is then warming up to 100~110 DEG C again, carries out reaction 5~6 hours, and acrylic acid cashew pnenolic aldehyde photosensitive resin is made,
Its viscosity is 1710mPas；
3) by after the solvent rotary evaporation in acrylic acid cashew pnenolic aldehyde photosensitive resin made from step (2), by 50g acrylic acid
Cashew pnenolic aldehyde photosensitive resin is added to the 2,4,6- trimethylbenzoy-dipheny for the photoinitiator that its mass ratio is 3%
Mixing in phosphine oxide (TPO), and be sufficiently stirred, obtain 3D printing cashew nut phenolic group photosensitive resin；
Performance test
3D printing obtained is spread evenly across in clean tinplate sheet with cashew nut phenolic group photosensitive resin (with a thickness of 100 μ
M), then it is put into 365nm ultraviolet light (100mW/cm2) irradiate and irradiated in lower ultra-violet curing case；3D printing is photosensitive with cashew nut phenolic group
The cure times of resin are 10s, and film completion of cure, surface is smooth.Resin film bending property 2mm does not occur slight crack, hardness
3B, 2 grades of adhesive force, the impact resistance of cured film reaches 75kgcm.It is printed as batten with the SLA 3D printer of Forms2,
The molding shrinkage of batten is 0.2%.
Embodiment 4
1) it using dimethylbenzene as solvent, is added 100g cashew nut shell liquid (CNSL), 4g hexa (H powder) is then added
A certain amount of distilled water reacts mixed system at 80~90 DEG C 1~3 hour, is then warming up to 130~140 DEG C of reflux again
Processing 1~2 hour is made anacardol formaldehyde condensation products (PCF)；
2) using 0.8g p-methyl benzenesulfonic acid as catalyst, 1g Isosorbide-5-Nitrae-hydroquinone is polymerization inhibitor, and 30g dimethylbenzene is solvent, into
After row mixing, 25g anacardol formaldehyde condensation products (PCF) and 75g methacrylic acid (MAA) is added, then in 80~90 DEG C of temperature
Under the conditions of reflow treatment 6 hours, be then warming up to 100~110 DEG C, carry out that the reaction was continued 5~6 hours, methacrylic acid is made
Cashew pnenolic aldehyde photosensitive resin, viscosity be 1711mPas；
3) by after the solvent rotary evaporation in methacrylic acid cashew pnenolic aldehyde photosensitive resin made from step (2), by 50g first
Base acrylic acid cashew pnenolic aldehyde photosensitive resin is added to photoinitiator 2- methyl -2- (4- morpholinyl) -1- that its mass ratio is 3%
It mixes, and is sufficiently stirred in [4- (methyl mercapto) phenyl] -1- acetone, 3D printing cashew nut phenolic group photosensitive resin is made.
Performance test
3D printing obtained is spread evenly across in clean tinplate sheet with cashew nut phenolic group photosensitive resin (with a thickness of 100 μ
M), then it is put into 365nm ultraviolet light (100mW/cm2) irradiate treatment with irradiation in lower ultra-violet curing case；3D printing cashew nut phenolic group
The cure times of photosensitive resin are 10s, and film completion of cure, surface is smooth.Resin film bending property 2mm does not occur slight crack,
Hardness 3B, 2 grades of adhesive force, the impact resistance of cured film reaches 55kgcm.It is printed as with the SLA 3D printer of Forms2
Batten, the molding shrinkage of batten are 0.5%.
Comparative example
1) it using dimethylbenzene as solvent, is added 100g cashew nut shell liquid (CNSL), 4g hexa (H powder) is then added
A certain amount of distilled water；React mixed system 1~3 hour at 80~90 DEG C, be warming up to 130~140 DEG C of reflow treatments 1~
It 2 hours, obtains anacardol formaldehyde condensation products (PCF), the viscosity of PCF is 2536mPas；
2) 2,4,6- trimethylbenzoyls of the photoinitiator for being by weight, 5% by 50g PCF and PCF mass ratio
In base-diphenyl phosphine oxide, it is sufficiently stirred to get comparative example cashew nut phenol resin is arrived；
3) comparative example cashew nut phenol resin is spread evenly across in clean tinplate sheet (with a thickness of 100 μm), is put into
365nm ultraviolet light (100mW/cm2) irradiates to be irradiated in lower ultra-violet curing case, and comparative example cashew nut phenol resin is uncured.With
The SLA 3D printer of Forms2 prints, non-printing shaping.
By the way that Examples 1 to 4 and comparative example 1 are compared, it can be seen that a photosensitive group is introduced in PCF, it can be with
The effectively ultra-violet curing ability of cashew nut phenol resin shortens the ultra-violet curing time.
The foregoing is merely of the invention for example, for a person skilled in the art, religion according to the present invention
Lead, without departing from the principles and spirit of the present invention all equivalent changes done according to scope of the present invention patent, repair
Change, replacement and variant, is all covered by the present invention.
Claims (10)
1. a kind of 3D printing preparation method of cashew nut phenolic group photosensitive resin, it is characterised in that: with anacardol and hexa-methylene four
Amine is that raw material is mixed, and after dimethylbenzene is then added as solvent mixing, anacardol formaldehyde condensation products are made；Again with toluene sulphur
Acid is catalyst, and Isosorbide-5-Nitrae-hydroquinone is polymerization inhibitor, and dimethylbenzene is solvent, adds it to anacardol formaldehyde condensation products and with light
In the mixture of quick group class monomer, cashew nut phenolic group photocuring performed polymer is made；Then after solvent being evaporated, by cashew nut phenolic group light
Curing prepolymer and photoinitiator are the ratio mixing of 100:0.1~10 in mass ratio, and after being sufficiently stirred, 3D can be obtained and beat
Print cashew nut phenolic group photosensitive resin.
2. a kind of preparation method of 3D printing cashew nut phenolic group photosensitive resin according to claim 1, it is characterised in that: institute
The anacardol stated derives from cashew nut shell liquid.
3. a kind of preparation method of 3D printing cashew nut phenolic group photosensitive resin according to claim 2, it is characterised in that: its
Specifically comprise the following steps:
(1) using dimethylbenzene as solvent, 100 parts of cashew nut shell liquids and 4 parts of hexas is added thereto, distillation is then added
Water, enable its 80~90 DEG C hybrid reaction 1~3 hour, then heat to 130~140 DEG C of reflow treatments 1~2 hour, be made waist
Fruit phenol formaldehyde condensation products；
(2) take 0.8 part of p-methyl benzenesulfonic acid as catalyst, 1 part of Isosorbide-5-Nitrae-hydroquinone as polymerization inhibitor, 30 parts of dimethylbenzene as molten
Agent is mixed, and then adds anacardol formaldehyde condensation products made from 25~50 parts of steps (2) and 50~75 parts with photosensitive base
Class monomer is mixed, and reflow treatment 6h under the conditions of 80~90 DEG C, then be warming up to 100~110 DEG C carry out that the reaction was continued 5~
6 hours, cashew nut phenolic group photocuring performed polymer is made；
(3) by after the solvent rotary evaporation in cashew nut phenolic group photocuring performed polymer made from step (2), then by itself and photoinitiator
It is thoroughly mixed in mass ratio for the ratio of 100:0.1~10, can be prepared by 3D printing cashew nut phenolic group photosensitive resin.
4. a kind of preparation method of 3D printing cashew nut phenolic group photosensitive resin according to claim 3, it is characterised in that: step
It suddenly is acrylic acid, methacrylic acid, acryloyl chloride, glycidyl methacrylate with photosensitive base class monomer described in (2)
One of.
5. a kind of preparation method of 3D printing cashew nut phenolic group photosensitive resin according to claim 3, it is characterised in that:
Photoinitiator described in step (3) includes 2- hydroxy-2-methyl -1- phenylacetone, 1- hydroxycyclohexyl phenyl ketone, 2- first
Base -2- (4- morpholinyl) -1- [4- (methyl mercapto) phenyl] -1- acetone, 2, the oxidation of 4,6- trimethylbenzoy-diphenies
Phosphine, 2, one of 4,6- trimethylbenzoyl phenyl phosphinic acid ethyl esters.
6. a kind of preparation method of 3D printing cashew nut phenolic group photosensitive resin according to claim 3, it is characterised in that: step
Suddenly the viscosity of cashew nut phenolic group photocuring performed polymer obtained is 1132~1711mPa s in (2).
7. a kind of preparation method of 3D printing cashew nut phenolic group photosensitive resin according to claim 3, it is characterised in that: step
Suddenly in (3) 3D printing obtained with cashew nut phenolic group photosensitive resin in a length of 365~405nm of ultraviolet light wave, uv power 100
~133mW/cm2Under conditions of lighting process the ultra-violet curing time be 1~100s.
8. answering to 3D printing cashew nut phenolic group photosensitive resin obtained by preparation method described in one of 7 according to claim 1
With, it is characterised in that: it is loaded into progress 3D printing product in 3D printing equipment.
9. application according to claim 8, it is characterised in that: photocuring 3 D-printing used by the 3D printing equipment
Technology is one of stereolithography apparatus technology, digital light projection technology, Laser Clad Deposition technology.
10. a kind of 3D printing cashew nut phenolic group photosensitive resin, it is characterised in that: its preparation as described in one of claim 1 to 7
Method is made.
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| CN110981905A (en) * | 2019-11-26 | 2020-04-10 | 江南大学 | Phosphorus-bromine-containing cardanol-based photosensitive resin, preparation method and application thereof |
| CN113912800A (en) * | 2021-10-21 | 2022-01-11 | 艾伦塔斯电气绝缘材料(珠海)有限公司 | Modified phenolic resin and preparation method and application thereof |
| CN114181446A (en) * | 2022-01-12 | 2022-03-15 | 北京新世纪京喜防水材料有限责任公司 | Polymer waterproof sheet, preparation method thereof and polymer waterproof coiled material |
| CN114516952A (en) * | 2022-01-26 | 2022-05-20 | 福建省腾龙工业公司 | Cardanol modified alkyd resin and preparation method and application thereof |
| CN114716671A (en) * | 2022-04-22 | 2022-07-08 | 深圳飞扬骏研新材料股份有限公司 | Preparation method of salt-fog-resistant polyaspartic acid ester, salt-fog-resistant polyaspartic acid ester and coating |
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| CN114516952A (en) * | 2022-01-26 | 2022-05-20 | 福建省腾龙工业公司 | Cardanol modified alkyd resin and preparation method and application thereof |
| CN114716671A (en) * | 2022-04-22 | 2022-07-08 | 深圳飞扬骏研新材料股份有限公司 | Preparation method of salt-fog-resistant polyaspartic acid ester, salt-fog-resistant polyaspartic acid ester and coating |
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| CN109867760B (en) | 2021-03-16 |
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