CN114426545A - 一种脂环族环氧树脂的制备方法 - Google Patents
一种脂环族环氧树脂的制备方法 Download PDFInfo
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- CN114426545A CN114426545A CN202011006779.XA CN202011006779A CN114426545A CN 114426545 A CN114426545 A CN 114426545A CN 202011006779 A CN202011006779 A CN 202011006779A CN 114426545 A CN114426545 A CN 114426545A
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- 125000002723 alicyclic group Chemical group 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 9
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- 239000003054 catalyst Substances 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002808 molecular sieve Substances 0.000 claims abstract description 17
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000010936 titanium Substances 0.000 claims abstract description 16
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- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 11
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 11
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- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 7
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
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- DMGCMUYMJFRQSK-UHFFFAOYSA-N 5-prop-1-en-2-ylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C(=C)C)CC1C=C2 DMGCMUYMJFRQSK-UHFFFAOYSA-N 0.000 claims description 3
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- HYFLWBNQFMXCPA-UHFFFAOYSA-N 1-ethyl-2-methylbenzene Chemical compound CCC1=CC=CC=C1C HYFLWBNQFMXCPA-UHFFFAOYSA-N 0.000 claims description 2
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- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
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- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 claims description 2
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- RWXPSIRAVCNFPR-UHFFFAOYSA-N spiro[4.4]non-3-ene Chemical compound C1CCCC21C=CCC2 RWXPSIRAVCNFPR-UHFFFAOYSA-N 0.000 claims description 2
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 11
- 239000002134 carbon nanofiber Substances 0.000 description 11
- 229910052710 silicon Inorganic materials 0.000 description 11
- 239000010703 silicon Substances 0.000 description 11
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- 229910001868 water Inorganic materials 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 9
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 4
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
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- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
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- 239000007864 aqueous solution Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
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- BQQUFAMSJAKLNB-UHFFFAOYSA-N dicyclopentadiene diepoxide Chemical compound C12C(C3OC33)CC3C2CC2C1O2 BQQUFAMSJAKLNB-UHFFFAOYSA-N 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 229910000514 dolomite Inorganic materials 0.000 description 2
- 239000010459 dolomite Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
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- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 description 1
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- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
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- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
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- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 description 1
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- WQVHBNPUCCOUSZ-UHFFFAOYSA-N cyclohexene;2-hydroperoxy-2-methylpropane Chemical group CC(C)(C)OO.C1CCC=CC1 WQVHBNPUCCOUSZ-UHFFFAOYSA-N 0.000 description 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
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- 229910001325 element alloy Inorganic materials 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- ITNVWQNWHXEMNS-UHFFFAOYSA-N methanolate;titanium(4+) Chemical compound [Ti+4].[O-]C.[O-]C.[O-]C.[O-]C ITNVWQNWHXEMNS-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
- 238000002444 silanisation Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/08—Bridged systems
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/10—Spiro-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/22—Di-epoxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/60—Synthesis on support
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Epoxy Compounds (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种脂环族环氧树脂的制备方法,采用钛硅分子筛为催化剂,惰性溶剂存在下,脂环族双烯烃和与有机过氧化物通过催化氧化反应生成脂环族环氧树脂。本发明提供的制备脂环族环氧树脂工艺,反应条件温和,产品收率高,废液排放量少,工艺操作安全简便,为合成脂环族环氧树脂提供了一条绿色反应工艺。
Description
技术领域
本发明属于催化氧化合成有机环氧化合物及烯烃催化氧化技术领域,具体的说,涉及一种以脂环族双烯烃原料,钛硅分子筛为催化剂,有机过氧化物为氧化剂,制备脂环族环氧树脂的方法。
背景技术
环氧树脂是一个分子中含有两个环氧基,并在适当的化学试剂存在下能形成三维交联网络状固化物的化合物总称。脂环族环氧树脂通常不含芳环等强紫外发色基团,当暴露于高压电弧下时分解产生二氧化碳、一氧化碳、水等小分子挥发物,不会生成游离碳导致形成导电通路,使其具有优良的耐高压漏电性能。优异的综合性能使脂环族环氧树脂近年来在超大规模集成电路封装、印制电路板制造、特种光固化涂料、耐高温电机绝缘材料等领域得到广泛应用。
现有技术中,包括二氧化双环戊二烯在内的许多脂环族环氧树脂一般采用过氧乙酸氧化法。反应所需的过氧乙酸通常现制,以乙酸、50%~80%双氧水为原料,在浓硫酸催化下制得,工艺危险性较高,生产规模较小。该工艺所用的乙酸大量过量,设备腐蚀严重,过量的乙酸容易导致环氧化物酸性开环生成副产物,反应产物需碱水多次洗涤,“三废”排放量多等缺点。
发明内容
为了解决现有合成脂环族环氧树脂的工艺缺陷,发明人发现,采用钛硅分子筛催化剂,过氧化氢异丙苯、过氧化氢叔丁醇等有机过氧化物为氧化剂,在温和的反应工艺条件下,可以高效合成二氧化双环戊二烯。通过实验,发明人还发现,将碳原子数为6~18的脂环族双烯烃替代双环戊二烯,在同样的条件下,可合成一系列脂环族环氧树脂。
本发明的技术方案具体介绍如下:
本发明提供了一种脂环族环氧树脂的制备方法,包括:以脂环族双烯烃为原料,有机过氧化物为氧化剂,在惰性溶剂存中,脂环族双烯烃、有机过氧化物与钛硅分子筛催化剂在反应器中充分接触下发生催化氧化反应,生成脂环族环氧树脂;
其中,所述钛硅分子筛催化剂为具有介孔特征的Ti-HMS分子筛催化剂,其组分包括:TiO2质量分数为0.10%~10.65%,纳米碳纤维质量分数为39.68%~62.90%,SiO2质量分数为28.17%~45.80%,氧化镁质量分数为0.01%~1.98%,硅烷基质量分数为0.44%~6.93%,所述的钛硅分子筛催化剂UV-vis谱图在220nm处有很强的吸收峰;
所述脂环族双烯烃与有机过氧化物摩尔比为1.0:1.8~1.0:2.5,与惰性溶剂体积比为1:4~1:30,催化氧化反应温度优选30~150℃、压力0~10MPa(表压)。
进一步的,所述的催化氧化反应温度为60~120℃、压力为0.3~6.0MPa(表压),所述的脂环族双烯烃与有机过氧化物摩尔比为1.0:2.0~1.0:2.2。
进一步的,所述的催化氧化反应采用间歇式反应工艺或固定床连续化反应工艺;采用间歇式反应工艺,催化剂用量与脂环族双烯烃质量比为0.01:100~20:100,反应时间为1~20小时;采用固定床连续化反应工艺,总物料体积空速为0.1~4.3h-1。
进一步的,所述的催化氧化反应采用间歇式反应工艺,催化剂与脂环族双烯烃的质量比为0.5:100~10:100,反应时间为3~6小时。
进一步的,所述的惰性溶剂选自环己烷、正己烷、庚烷、辛烷、壬烷、癸烷、十一烷、苯、甲苯、乙苯、甲乙苯、二甲苯、异丙苯、石油醚中任意一种。
进一步的,所述的有机过氧化物优选过氧化氢异丙苯、过氧化氢叔丁醇或过氧氢叔戊醇。
进一步的,所述的脂环族双烯烃为每一分子中的碳原子数6~18的脂环族双烯烃。
进一步的,所述的每一分子中碳原子数6~18的脂环族双烯烃优选以下化合物中的任意一种:双环戊二烯、三聚环戊二烯、2,5-降冰片二烯、5-乙烯基-2-降冰片烯、5-亚乙基-2-降冰片烯、5-异丙烯基-2-降冰片烯、4-乙烯基-1-环己烯、苧烯、3,3`-二联环己烯、3,3`-二联环戊烯、螺双环己烯或螺双环戊烯。这些化合物分子结构式如下所示:
进一步的,所述钛硅分子筛催化剂为具有介孔特征的Ti-HMS分子筛催化剂,其组分包括:TiO2质量分数为2.57%~6.42%,纳米碳纤维质量分数为48.95%~62.90%,SiO2质量分数为28.17%~38.87%,氧化镁质量分数为0.01%~0.83%,硅烷基质量分数为0.44%~6.41%。
上述所提及的钛硅分子筛催化剂,其制备方法如下:
a)在惰性气氛下,将硅源、钛源、模板剂溶解在水和有机醇的混合溶剂中,室温搅拌晶化0.5~10小时,加入纳米碳纤维继续搅拌10~72小时,然后于150~200℃晶化1~7天,结晶产物经分离、洗涤和干燥,得到纳米碳纤维负载的Ti-HMS;
b)将纳米碳纤维负载的Ti-HMS投入到含Mg(OH)2、MgO、MgCO3、4MgCO3。Mg(OH)2.5H2O、白云石(MgCO3.CaCO3)中任意一种或几种混合物的水溶液中,室温搅拌10~48小时后,分离出固体,水洗,至水洗液呈中性,干燥,然后在惰性气氛中,于300~1000℃焙烧2~20小时,得到含镁化合物改性、纳米碳纤维为载体的Ti-HMS催化剂母体;
c)将Ti-HMS催化剂母体在25~300℃的温度下用有机硅溶液处理0.5~100小时;有机硅的用量为Ti-HMS催化剂母体重量的10%~70%;然后过滤分离出固体催化剂,用惰性溶剂洗涤,再将固体催化剂于压力0.133~1.33KPa,温度80~200℃的环境中烘烤10~24h,制得含镁化合物改性的Ti-HMS/纳米碳纤维复合催化剂。
进一步的,步骤a)中,硅源为正硅酸酯或烃基硅酸酯中的一种或两种;钛源为钛酸酯;模板剂为通式RNH2的有机胺,R为6~18个碳原子的链烃基;RNH2和硅源中的Si的摩尔比为0.01~0.3:1,硅源中的Si与钛源中的Ti的摩尔比为5:1~500:1,水与硅源摩尔比为4~20:1,醇和硅源的体积比为1~4:1,纳米碳纤维与硅源的摩尔比为5~20:1。
进一步的,所用的钛酸酯选自选自钛酸四甲酯、钛酸四乙酯、钛酸四丙酯、钛酸四丁酯、钛酸四异丁酯中的任意一种。
进一步的,步骤a)中,所用的纳米碳纤维,是由含碳气源,优选CO、CH4、C2H6、C3H8中的任意一种为反应原料,选用周期表第Ⅷ族元素,更优选Fe、Co、Ni中任意一种单金属元素或多种元素合金为催化剂,通过含碳气源催化裂解反应形成的纳米碳纤维,纳米碳纤维催化生长温度为550~650℃。
进一步的,步骤b)中,纳米碳纤维负载的Ti-HMS与含镁化合物水溶液的体积比为1:1~1:3,MgO、Mg(OH)2、MgCO3、4MgCO3。Mg(OH)2.5H2O、白云石中任意一种或几种混合物与步骤a)所用的硅源的摩尔比为0.01:100~7:100;焙烧温度为400~800℃,焙烧时间为3~8小时。
进一步的,步骤c)中,所用的有机硅溶液,有机硅选自卤硅烷、硅氮烷或甲硅烷基胺中的任意一种。
进一步的,步骤c)中,有机硅选自三甲基氯硅烷、三乙基氯化硅、六甲基二硅氮烷或N-三甲基硅烷基咪唑中的任意一种。
进一步的,步骤c)中,所用的有机硅溶液,溶剂选自苯、甲苯、异丙苯、乙苯、环己烷、正庚烷、辛烷、十二烷中的任意一种或几种混合物。
进一步的,步骤c)中,用惰性溶剂洗涤,包括:用甲苯、苯或烷烃惰性溶剂对固体催化剂洗涤3次,每次洗涤所用的惰性溶剂体积是固体催化剂体积5~10倍。
与现有技术相比,本发明具有以下优点:
按照本发明提供的制备方法,用于脂环族环氧树脂合成合成,催化剂活性好,寿命长,产物收率高,产品易分离,反应条件温和,可以采用固定床连续化反应工艺,反应工艺安全性大大提高,为工业化生产脂环族环氧树脂提供了一种绿色环保反应工艺。
具体实施例
以下以实施例进一步说明本发明,但本发明并不局限于实施例。本专利说明书中的脂环族环氧树脂产物收率定义:
环氧树脂反应收率=反应产物中的环氧树脂摩尔数/参与反应的脂环族双烯烃原料摩尔数*100%。
实施例1:制备钛硅分子筛催化剂
在室温和搅拌条件下,反应器中依次加15.6克十六胺加入到110ml水和100毫升乙醇中,搅拌;将溶于40毫升乙醇的65克正硅酸乙酯、0.12克钛酸乙酯加入到上述溶液中,搅拌50分钟,晶化10小时,投入18.7克纳米碳纤维,继续搅拌10~72小时,反应器升温,反应物料在200℃晶化2天,过滤得到固体,用乙醇萃取催化剂中的模板剂,然后纯水洗涤,直到淋洗液呈中性。将洗涤后的固体在110℃烘干15小时后,得到纳米碳纤维为载体的Ti-HMS。
将上述纳米碳纤维为载体的Ti-HMS固体中加入3倍体积纯水,1.2克Mg(OH)2,室温,搅拌48小时,分离出固体,纯水洗涤,直到水洗液呈中性,80℃干燥30小时,然后450℃,氦气氛中焙烧18小时,得到含镁化合物改性、纳米碳纤维为载体的Ti-HMS;
将上述制备的粉末催化剂样品压片成型后,破碎、筛分,取20~50目的颗粒50克,投入到反应器中,然后再向反应器中加15.5克三甲基氯硅烷、200毫升甲苯,搅拌,反应温度120℃进行硅烷化12小时,终止反应,取出固体催化剂,甲苯淋洗后,在温度90℃,***压力0.133KPa的真空***干燥30小时。
实施例2~13:釜式反应器,催化氧化合成脂环族环氧树脂
取钛硅分子筛催化剂、有机过氧化物、溶剂,按工艺要求投料到500毫升反应器中,考察温度、压力、物料配比、反应时间对环氧树脂产物收率的影响,实施例2~13所用的催化剂组成见表1(制备方法参考实施例1),所用的脂环族双烯烃和有机过氧化物见表2,实验结果见表3。
表1催化剂质量百分百组成
*注:C—表示纳米碳纤维。
表2釜式反应合成环氧树脂所用的烯烃原料和过氧化物
实施例 | 脂环族双烯烃 | 有机过氧化物 |
2 | 双环戊二烯 | 过氧化氢苯甲酰 |
3 | 三聚环戊二烯 | 过氧化氢叔丁醇 |
4 | 2,5-降冰片二烯 | 过氧化氢叔戊醇 |
5 | 5-乙烯基-2-降冰片烯 | 过氧化氢异丙苯 |
6 | 5-亚乙基-2-降冰片烯 | 过氧化氢异丙苯 |
7 | 5-异丙烯基-2-降冰片烯 | 过氧化氢异丙苯 |
8 | 4-乙烯基-1-环己烯 | 过氧化氢异丙苯 |
9 | 苧烯 | 过氧化氢叔丁醇 |
10 | 3,3`-二联环己烯 | 过氧化氢叔丁醇 |
11 | 3,3`-二联环戊烯 | 过氧化氢异丙苯 |
12 | 螺双环己烯 | 过氧化氢异丙苯 |
13 | 螺双环戊烯 | 过氧化氢异丙苯 |
表3釜式反应合成环氧树脂工艺条件
实施例14~21:固定床催化氧化反应工艺制备脂环族环氧树脂
催化剂30克,填装到100毫升等温固定床反应中器,有机过氧化物为氧化剂,反应料液通过计量泵打入到反应器中,所用的催化剂组成见表4,所用的脂环族双烯烃原料和有机过氧化物见表5,分别考察温度、压力、物料配比、空速对反应产物收率的影响,实验结果见表6,实施例2~21所对应的环氧树脂结构见表7。
表4催化剂质量百分组成
*注:C—表示纳米碳纤维。
表5固定床反应工艺合成环氧树脂所用的烯烃原料和过氧化物
实施例 | 脂环族环烯烃 | 有机过氧化物 |
14 | 双环戊二烯 | 过氧化氢异丙苯 |
15 | 5-乙烯基-2-降冰片烯 | 过氧化氢异丙苯 |
16 | 5-异丙烯基-2-降冰片烯 | 过氧化氢异丙苯 |
17 | 4-乙烯基-1-环己烯 | 过氧化氢叔戊醇 |
18 | 苧烯 | 过氧化氢叔丁醇 |
19 | 3,3`-二联环戊烯 | 过氧化氢异丙苯 |
20 | 螺双环己烯 | 过氧化氢异丙苯 |
21 | 螺双环戊烯 | 过氧化氢异丙苯 |
表6固定床反应合成环氧树脂工艺条件
表7环氧树脂结构
以上已对本发明创造的较佳实施例进行了具体说明,但本发明创造并不限于所述实施例,熟悉本领域的技术人员在不违背本发明创造精神的前提下还可作出种种的等同的变型或替换,这些等同的变型或替换均包含在本申请权利要求所限定的范围内。
Claims (9)
1.一种脂环族环氧树脂的制备方法,包括:以脂环族双烯烃为原料,有机过氧化物为氧化剂,在惰性溶剂存中,脂环族双烯烃、有机过氧化物与钛硅分子筛催化剂在反应器中充分接触下发生催化氧化反应,生成脂环族环氧树脂;
其中,所述钛硅分子筛催化剂为具有介孔特征的Ti-HMS分子筛催化剂,其组分包括:TiO2质量分数为0.10%~10.65%,纳米碳纤维质量分数为39.68%~62.90%,SiO2质量分数为28.17%~45.80%,氧化镁质量分数为0.01%~1.98%,硅烷基质量分数为0.44%~6.93%;所述催化剂UV-vis谱图在220nm处有很强的吸收峰;
所述催化氧化反应温度为30~150℃、压力0~10MPa(表压);脂环族双烯烃与有机过氧化物摩尔比为1.0:2.0~1.0:2.5,脂环族双烯烃与惰性溶剂体积比为1:4~1:30。
2.根据权利要求1所述的方法,其特征在于:所述催化氧化反应温度为60~120℃、压力为0.3~6MPa(表压),脂环族双烯烃与有机过氧化物摩尔比为1.0:2.0~1.0:2.2。
3.根据权利要求1所述的方法,其特征在于:所述催化氧化反应采用间歇式反应工艺或固定床连续化反应工艺;采用间歇式反应工艺,催化剂用量与脂环族双烯烃质量比为0.01:100~20:100,反应时间为1~20小时;采用固定床连续化反应工艺,总物料体积空速为0.1~4.3h-1。
4.根据权利要求3所述的方法,其特征在于:所述采用间歇反应工艺,催化剂用量与脂环族双烯烃的质量比为0.5:100~10:100,反应时间为3~6小时。
5.根据权利要求1所述的方法,其特征在于:所述惰性溶剂选自庚烷、己烷、辛烷、壬烷、癸烷、十一烷、苯、甲苯、乙苯、甲乙苯、二甲苯、异丙苯、石油醚中的任一种。
6.根据权利要求1所述的方法,其特征在于:所述脂环族双烯烃选自每一分子中的碳原子数为6~18的脂环族双烯烃。
7.根据权利要求6所述的方法,其特征在于:所述每一分子中碳原子数为6~18的脂环族双烯烃选自双环戊二烯、三聚环戊二烯、2,5-降冰片二烯、5-乙烯基-2-降冰片烯、5-亚乙基-2-降冰片烯、5-异丙烯基-2-降冰片烯、4-乙烯基-1-环己烯、苧烯、3,3`—二联环己烯、3,3`—二联环戊烯、螺双环己烯、螺双环戊烯中的任一种。
8.根据权利要求1所述的方法,其特征在于:所述有机过氧化物选用过氧化氢异丙苯、过氧化氢叔丁醇、过氧化氢叔戊醇中任意一种。
9.根据权利要求1所述的方法,其特征在于:所述钛硅分子筛催化剂为具有介孔特征的Ti-HMS分子筛催化剂,其组分包括:TiO2质量分数为2.57%~6.42%,纳米碳纤维质量分数为48.95%~62.90%,SiO2质量分数为28.17%~38.87%,氧化镁质量分数为0.01%~0.83%,硅烷基质量分数为0.44%~6.41%。
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