CN108559060A - A kind of preparation method of modifying epoxy resin by organosilicon - Google Patents
A kind of preparation method of modifying epoxy resin by organosilicon Download PDFInfo
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- 239000003822 epoxy resin Substances 0.000 title claims abstract description 82
- 229920000647 polyepoxide Polymers 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- -1 dimethyldimethoxysiloxane, methylvinyldimethoxysiloxane Chemical class 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 229920001296 polysiloxane Polymers 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- 229920002545 silicone oil Polymers 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 15
- 239000003921 oil Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000009477 glass transition Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- ZLNAFSPCNATQPQ-UHFFFAOYSA-N ethenyl-dimethoxy-methylsilane Chemical compound CO[Si](C)(OC)C=C ZLNAFSPCNATQPQ-UHFFFAOYSA-N 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 125000003700 epoxy group Chemical group 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical class C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- ZUGOSPHJWZAGBH-UHFFFAOYSA-N CO[SiH](OC)C=C Chemical compound CO[SiH](OC)C=C ZUGOSPHJWZAGBH-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct 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
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 229940008099 dimethicone Drugs 0.000 description 1
- PKTOVQRKCNPVKY-UHFFFAOYSA-N dimethoxy(methyl)silicon Chemical compound CO[Si](C)OC PKTOVQRKCNPVKY-UHFFFAOYSA-N 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000004100 electronic packaging Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000007039 two-step reaction Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- 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
- C08G59/14—Polycondensates modified by chemical after-treatment
- C08G59/1433—Polycondensates modified by chemical after-treatment with organic low-molecular-weight compounds
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Epoxy Resins (AREA)
- Silicon Polymers (AREA)
Abstract
本发明公开了一种有机硅改性环氧树脂的制备方法。该方法将环氧树脂和第一催化剂混合，在70～120℃的油浴锅中搅拌并滴加有机硅单体A，待有机硅单体滴加完毕后，再滴加蒸馏水，反应4～8h后，得到第一步改性产物B；所述的有机硅单体A为二甲基二甲氧基硅氧烷、甲基乙烯基二甲氧基硅氧烷和甲基苯基二甲氧基硅氧烷中的一种；50～90℃的油浴搅拌条件下，在所述改性产物B中滴加有机硅单体C，加入第二催化剂，反应30～90min后得到有机硅改性环氧树脂。本发明制备了耐热性能和韧性良好的有机硅改性环氧树脂，本发明工艺简单、环境友好、改性后的环氧树脂可采用普通的环氧树脂固化工艺，适合于工业化生产。
The invention discloses a preparation method of organosilicon modified epoxy resin. In this method, epoxy resin and the first catalyst are mixed, stirred in an oil bath at 70-120°C, and organosilicon monomer A is added dropwise. After 8h, the modified product B of the first step is obtained; the organosilicon monomer A is dimethyldimethoxysiloxane, methylvinyldimethoxysiloxane and methylphenyldimethylsiloxane One of the oxysiloxanes; under the condition of stirring in an oil bath at 50-90°C, add organosilicon monomer C dropwise to the modified product B, add the second catalyst, and react for 30-90 minutes to obtain organosilicon Modified epoxy resin. The invention prepares the organosilicon modified epoxy resin with good heat resistance and toughness. The invention has the advantages of simple process, environmental friendliness, common epoxy resin curing process can be adopted for the modified epoxy resin, and is suitable for industrialized production.
Description
技术领域technical field
本发明涉及一种有机硅改性环氧树脂的制备方法，特别涉及用于环氧树脂在固化后质脆及耐热性能不佳的缺点所开发的具有较好韧性及热稳定性能有机硅改性环氧树脂的制备方法。The present invention relates to a preparation method of silicone-modified epoxy resin, in particular to a silicone-modified epoxy resin with good toughness and thermal stability developed for the shortcomings of epoxy resin after curing, which is brittle and poor in heat resistance. Preparation method of permanent epoxy resin.
背景技术Background technique
环氧树脂是一种非常常见的热固性树脂，是聚合物复合材料研究应用的中一种重要的基体材料，被广泛应用于层压材料、胶粘剂、电子封装材料及涂料等行业。其具有了优良的物理及化学性能，如较好的尺寸稳定性，固化后产品的收缩率小、优良的耐腐蚀性能、电绝缘性能等，是一种综合性能比较优异的树脂。不过环氧树脂在固化开环后会形成大型的三维网状结构，这导致了其固化产物的内应力大，质脆，力学性能不好，尤其是抗冲击能力较差，很大地制约了环氧树脂在高端领域的应用，而且随着相关行业的发展，对环氧树脂耐热性能的要求也越来越高，这使高韧性、高耐热成为环氧树脂高性能化研究的一个热门方向，Epoxy resin is a very common thermosetting resin. It is an important matrix material in the research and application of polymer composite materials. It is widely used in lamination materials, adhesives, electronic packaging materials and coatings and other industries. It has excellent physical and chemical properties, such as good dimensional stability, small shrinkage of the cured product, excellent corrosion resistance, electrical insulation properties, etc., and is a resin with excellent comprehensive properties. However, epoxy resin will form a large three-dimensional network structure after curing and ring opening, which leads to large internal stress, brittle quality and poor mechanical properties of the cured product, especially poor impact resistance, which greatly restricts the use of rings. The application of epoxy resin in high-end fields, and with the development of related industries, the requirements for the heat resistance of epoxy resin are getting higher and higher, which makes high toughness and high heat resistance a hot topic in the research of high-performance epoxy resin direction,
在很多关于有机硅改性环氧树脂的研究中，虽然经过改性后环氧树脂的韧性都能得到有效提高，但同时大多伴随着环氧树脂热稳定性能，如玻璃化转变温度的下降。In many studies on silicone-modified epoxy resins, although the toughness of epoxy resins can be effectively improved after modification, most of them are accompanied by the thermal stability of epoxy resins, such as the decrease of glass transition temperature.
发明内容Contents of the invention
本发明的目的是提供一种新型有机硅改性环氧树脂的合成制备方法，为了改善环氧树脂在固化后的热稳定性能不佳及韧性较差的问题。本发明在实现环氧树脂的增韧的基础上，还能使环氧树脂的热稳定性能得以提高。The purpose of the present invention is to provide a method for the synthesis and preparation of a novel organosilicon-modified epoxy resin, in order to improve the problems of poor thermal stability and poor toughness of the epoxy resin after curing. On the basis of realizing the toughening of the epoxy resin, the invention can also improve the thermal stability of the epoxy resin.
本发明所采用的技术方案是：The technical scheme adopted in the present invention is:
一种有机硅改性环氧树脂的制备方法，包括如下步骤：A preparation method of organosilicon modified epoxy resin, comprising the steps of:
1)将环氧树脂和第一催化剂混合，在70～120℃的油浴锅中搅拌并滴加有机硅单体A，待有机硅单体滴加完毕后，再滴加蒸馏水，反应4～8h后，得到第一步改性产物B；所述的有机硅单体A为二甲基二甲氧基硅氧烷、甲基乙烯基二甲氧基硅氧烷和甲基苯基二甲氧基硅氧烷中的一种；所述的第一催化剂为二月桂酸二丁基锡和/或钛酸酯；1) Mix the epoxy resin and the first catalyst, stir in an oil bath at 70-120°C and add the organosilicon monomer A dropwise. After 8h, the modified product B of the first step is obtained; the organosilicon monomer A is dimethyldimethoxysiloxane, methylvinyldimethoxysiloxane and methylphenyldimethylsiloxane One of oxysiloxanes; the first catalyst is dibutyltin dilaurate and/or titanate;
2)50～90℃的油浴搅拌条件下，在所述改性产物B中滴加有机硅单体C，加入第二催化剂，反应30～90min后得到有机硅改性环氧树脂；所述的有机硅单体C为含氢双封头和含氢硅油中的一种或两者的混合物；所述的第二催化剂为氯铂酸、Karstedt催化剂和钛酸酯中的一种。2) Under the condition of stirring in an oil bath at 50-90°C, dropwise add organosilicon monomer C to the modified product B, add a second catalyst, and react for 30-90 minutes to obtain an organosilicon-modified epoxy resin; The organosilicon monomer C is one or a mixture of hydrogen-containing double head and hydrogen-containing silicone oil; the second catalyst is one of chloroplatinic acid, Karstedt catalyst and titanate.
为进一步实现本发明目的，优选地，所述的环氧树脂为双份A型环氧树脂E44或双份A型环氧树脂E51。In order to further realize the object of the present invention, preferably, the epoxy resin is two-part A-type epoxy resin E44 or two-part A-type epoxy resin E51.
优选地，环氧树脂与有机硅单体A的质量比为100：5～15。Preferably, the mass ratio of the epoxy resin to the silicone monomer A is 100:5-15.
优选地，所述的有机硅单体A与蒸馏水的摩尔比为1：0.5～1.5。Preferably, the molar ratio of the organosilicon monomer A to distilled water is 1:0.5-1.5.
优选地，第一催化剂加入量为步骤1)原料质量的0.1～1wt％。Preferably, the amount of the first catalyst added is 0.1-1 wt% of the mass of the raw material in step 1).
优选地，所述的有机硅单体A与有机硅单体C的摩尔比为1：0.1～2。Preferably, the molar ratio of the organosilicon monomer A to the organosilicon monomer C is 1:0.1-2.
优选地，步骤1)所述的搅拌为使用机械搅拌器或者磁力搅拌器，搅拌速率为300～600rpm。Preferably, the stirring described in step 1) uses a mechanical stirrer or a magnetic stirrer, and the stirring rate is 300-600 rpm.
优选地，步骤2)所述的第二催化剂的添加量为步骤2)原料质量的100～1000ppm。Preferably, the amount of the second catalyst added in step 2) is 100-1000 ppm of the mass of the raw material in step 2).
优选地，步骤1)和步骤2)原料的纯度为分析纯及以上纯度。Preferably, the purity of the raw materials in step 1) and step 2) is analytical purity or above.
由于有机硅的Si-0-Si链段具有比环氧树脂主链更好的柔性，常常用于环氧树脂的增韧改性，传统的改性方法多采用有机硅中的活性官能团与环氧树脂的环氧基团发生开环反应从而实现两者的结合改性，然而环氧基的消耗以及大分子有机硅的引入也导致环氧树脂在实现增韧的同时交联密度出现下降，进而造成玻璃化转变温度的下降。本发明通过选取特殊的有机硅单体A，在不消耗环氧基的情况对环氧树脂进行接枝改性，实现环氧树脂的增韧，同时由于单体A中特殊官能团的相互作用以及与单体C的反应可以进一步提高环氧树脂固化体系的交联密度，从而实现环氧树脂玻璃化温度的上升。Since the Si-0-Si segment of silicone has better flexibility than the main chain of epoxy resin, it is often used for toughening modification of epoxy resin. Traditional modification methods mostly use active functional groups and rings in silicone. The epoxy group of the epoxy resin undergoes a ring-opening reaction to realize the combined modification of the two. However, the consumption of the epoxy group and the introduction of macromolecular silicone also lead to a decrease in the crosslinking density of the epoxy resin while achieving toughness. This in turn causes a drop in the glass transition temperature. In the present invention, by selecting a special organosilicon monomer A, the epoxy resin is grafted and modified without consuming epoxy groups, so as to realize the toughening of the epoxy resin. The reaction with monomer C can further increase the cross-linking density of the epoxy resin curing system, thereby achieving an increase in the glass transition temperature of the epoxy resin.
相对于现有技术，本发明的优点在于：Compared with the prior art, the present invention has the advantages of:
1)本发明有机硅单体A为二甲基二甲氧基硅氧烷、甲基乙烯基二甲氧基硅氧烷和甲基苯基二甲氧基硅氧烷中的一种，通过选取特殊的有机硅单体A，在不消耗环氧基的情况对环氧树脂进行接枝改性，同时由于有机硅单体A中双键官能团的相互作用以及与有机硅单体C(有机硅单体C为含氢双封头和含氢硅油中的一种或两者的混合物)的反应可以进一步提高环氧树脂固化体系的交联密度，从而在实现环氧树脂的增韧的同时，有效地提高了环氧树脂玻璃化温度。1) The organosilicon monomer A of the present invention is one of dimethyldimethoxysiloxane, methylvinyldimethoxysiloxane and methylphenyldimethoxysiloxane, through Select a special silicone monomer A to graft and modify the epoxy resin without consuming epoxy groups. At the same time, due to the interaction of the double bond functional group in the silicone monomer A and the The reaction of silicon monomer C (one or both of hydrogen-containing double-caps and hydrogen-containing silicone oil) can further increase the crosslinking density of the epoxy resin curing system, thereby achieving the toughening of the epoxy resin while , effectively increasing the glass transition temperature of epoxy resin.
2)本发明采用缩聚和加成的两步反应制备的新型有机硅改性环氧树脂，其不仅能提高环氧树脂的耐热性能，而且也能实现对环氧树脂的增韧效果。固化后的改性环氧树脂的DSC测试表明，经过有机硅改性后的环氧树脂的玻璃化温度比未改性的有了明显提高。同时力学性能测试表面，经过改性后的环氧树脂的韧性比未改性之前也有了明显提高。2) The present invention adopts the novel organosilicon-modified epoxy resin prepared by the two-step reaction of polycondensation and addition, which can not only improve the heat resistance of epoxy resin, but also realize the toughening effect on epoxy resin. The DSC test of the cured modified epoxy resin shows that the glass transition temperature of the silicone modified epoxy resin is significantly higher than that of the unmodified epoxy resin. At the same time, the mechanical performance test surface shows that the toughness of the modified epoxy resin has also been significantly improved compared with that before the modification.
3)本发明不产生有毒有害的气体或副产物，绿色环保，原料转化率高。3) The present invention does not produce toxic and harmful gases or by-products, is environmentally friendly, and has a high conversion rate of raw materials.
4)本发明工艺简单，对仪器设备及反应条件的要求不高，在120℃以下常压即可反应，反应周期短，有利于工业化的生产应用。4) The process of the present invention is simple, does not require high equipment and reaction conditions, can react at normal pressure below 120° C., and has a short reaction cycle, which is beneficial to industrial production and application.
具体实施方式Detailed ways
下面结合具体实施例对本发明作进一步描述，但本发明不局限于以下实施例。此外应理解，在阅读了本发明的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样属于本发明所附权利要求书所限定的范围。The present invention will be further described below in conjunction with specific examples, but the present invention is not limited to the following examples. In addition, it should be understood that after reading the content of the present invention, those skilled in the art can make various changes or modifications to the present invention, and these equivalent forms also belong to the scope defined by the appended claims of the present invention.
实施例1Example 1
按照反应物的配比，取100g双份A型环氧树脂E44和0.1g的二月桂酸二丁基锡置于装有冷凝回流和恒压滴液漏斗的三口烧瓶中，恒压漏斗中装有8g的甲基乙烯基二甲氧基硅烷，在70℃的油浴，600rpm转速的机械搅拌中缓慢滴加甲基乙烯基二甲氧基硅烷，待甲基乙烯基二甲氧基硅烷滴加完毕后，再滴加约1g的蒸馏水，反应4h后即得到第一步改性产物。在第一步改性产物的基础上，在60℃的油浴，600rpm转速搅拌中继续滴加1g的含氢双封头，在300ppm的氯铂酸催化下反应30min后即得到有机硅改性环氧树脂。According to the proportioning of reactant, the dibutyltin dilaurate of 100g two parts of A-type epoxy resin E44 and 0.1g is placed in the there-necked flask equipped with condensing reflux and constant pressure dropping funnel, and 8g is housed in the constant pressure funnel Methylvinyldimethoxysilane, slowly add methylvinyldimethoxysilane dropwise in an oil bath at 70°C with mechanical stirring at a speed of 600rpm, and wait until the addition of methylvinyldimethoxysilane is complete Finally, about 1 g of distilled water was added dropwise, and the modified product of the first step was obtained after 4 hours of reaction. On the basis of the modified product in the first step, continue to drop 1g of hydrogen-containing double head in an oil bath at 60°C and stir at 600rpm, and react under the catalysis of 300ppm chloroplatinic acid for 30min to obtain the organosilicon modification epoxy resin.
本发明所得的最终产物与未改性的环氧树脂的红外光谱对比如图1所示。3520cm-1处环氧树脂羟基振动吸收峰的减弱以及1100cm-1处新的Si-O-Si吸收峰的出现证明了改性反应的成功进行。The infrared spectrum comparison between the final product obtained in the present invention and the unmodified epoxy resin is shown in Figure 1. The weakening of the epoxy resin hydroxyl vibration absorption peak at 3520cm -1 and the appearance of a new Si-O-Si absorption peak at 1100cm -1 proved the success of the modification reaction.
相对于未改性的环氧树脂，本发明所得的改性环氧树脂的无缺口冲击强度提升了51.2％，有效地实现了环氧树脂的增韧。冲击强度测试标准为GB/T 2567-2008。Compared with the unmodified epoxy resin, the unnotched impact strength of the modified epoxy resin obtained by the invention is increased by 51.2%, and the toughening of the epoxy resin is effectively realized. The impact strength test standard is GB/T 2567-2008.
相对于未改性的环氧树脂，本发明所得的改性环氧树脂的玻璃化转变温度提高了16.2℃。玻璃化转变温度采用DSC分析测定，测试的升温和冷却速率均为10℃/min，试验温度范围为30-200℃。测试在氮气气氛下进行，氮气流速为50mL/min。图2为测试所得的差式扫描量热分析曲线(DSC)曲线，未改性的环氧树脂固化物用EP表示，经有机硅改性的环氧树脂固化物用aEP表示。从DSC曲线中可以看出，在升温过程中会出现一个向吸热方向的阶梯，这个阶梯对应的是高聚物无定形部分从冻结状态到解冻状态的一种松弛过程，对应的温度称之为玻璃化转变温度。从两条曲线的对比可以看出，本发明所得的改性环氧树脂对应的阶梯向高温方向移动了，说明经过改性后环氧树脂的玻璃化转变温度得到了提高。Compared with the unmodified epoxy resin, the glass transition temperature of the modified epoxy resin obtained in the present invention is increased by 16.2°C. The glass transition temperature is determined by DSC analysis, the heating and cooling rates of the test are both 10°C/min, and the test temperature range is 30-200°C. The test was carried out under a nitrogen atmosphere with a nitrogen flow rate of 50 mL/min. Figure 2 is the differential scanning calorimetry curve (DSC) curve obtained from the test. The unmodified epoxy resin cured product is represented by EP, and the silicone-modified epoxy resin cured product is represented by aEP. It can be seen from the DSC curve that there will be a step in the direction of heat absorption during the heating process. This step corresponds to a relaxation process of the amorphous part of the polymer from the frozen state to the thawed state. The corresponding temperature is called is the glass transition temperature. From the comparison of the two curves, it can be seen that the step corresponding to the modified epoxy resin obtained in the present invention moves toward the high temperature direction, indicating that the glass transition temperature of the modified epoxy resin has been improved.
实施例2Example 2
按照反应物的配比，取100g双份A型环氧树脂E51和0.2g的钛酸酯置于装有冷凝回流和恒压滴液漏斗的三口烧瓶中，恒压漏斗中装有9g的甲基乙烯基二甲氧基硅烷，在80℃的油浴，500rpm转速的机械搅拌中缓慢滴加甲基乙烯基二甲氧基硅烷，待甲基乙烯基二甲氧基硅烷滴加完毕后，再滴加约1.5g的蒸馏水，反应5h后即得到第一步改性产物。在第一步改性产物的基础上，在70℃的油浴，600rpm转速搅拌中继续滴加3g的含氢硅油，在500ppm的Karstedt催化剂催化下反应60min后即得到有机硅改性环氧树脂。According to the ratio of the reactants, get 100g double parts of A-type epoxy resin E51 and 0.2g of titanate and place it in a three-necked flask equipped with condensing reflux and a constant pressure dropping funnel, and 9g of formazan is housed in the constant pressure funnel. Vinyl dimethoxysilane, in an oil bath at 80°C, slowly add methyl vinyl dimethoxy silane dropwise in a mechanical stirrer at 500rpm, after the methyl vinyl dimethoxy silane is added dropwise, Then about 1.5 g of distilled water was added dropwise, and the modified product of the first step was obtained after 5 hours of reaction. On the basis of the modified product in the first step, continue to drop 3g of hydrogen-containing silicone oil in an oil bath at 70°C and stir at 600rpm, and react for 60min under the catalysis of 500ppm Karstedt catalyst to obtain a silicone-modified epoxy resin .
实施例3Example 3
按照反应物的配比，取100g双份A型环氧树脂E44和0.3g的钛酸酯置于装有冷凝回流和恒压滴液漏斗的三口烧瓶中，恒压漏斗中装有10g的二甲基二甲氧基硅烷，在90℃的油浴，300rpm转速的机械搅拌中缓慢滴加二甲基二甲氧基硅烷，待二甲基二甲氧基硅烷滴加完毕后，再滴加约1g的蒸馏水，反应6h后即得到第一步改性产物。在第一步改性产物的基础上，在80℃的油浴，400rpm转速搅拌中继续滴加15g的含氢双封头，在400ppm的Karstedt催化剂催化下反应50min后即得到有机硅改性环氧树脂。According to the proportioning of reactant, get 100g two-part A-type epoxy resin E44 and the titanate of 0.3g and place in the there-necked flask equipped with condensing reflux and constant pressure dropping funnel, 10g of dimethicone is housed in the constant pressure funnel For methyldimethoxysilane, add dimethyldimethoxysilane slowly in an oil bath at 90°C with mechanical stirring at a speed of 300rpm. After the addition of dimethyldimethoxysilane is completed, add dropwise About 1g of distilled water, after 6 hours of reaction, the modified product of the first step can be obtained. On the basis of the modified product in the first step, continue to drop 15g of hydrogen-containing double head in an oil bath at 80°C while stirring at 400rpm, and react for 50min under the catalysis of 400ppm Karstedt catalyst to obtain the silicone modified ring oxygen resin.
实施例4Example 4
按照反应物的配比，取100g双份A型环氧树脂E51和1g的二月桂酸二丁基锡置于装有冷凝回流和恒压滴液漏斗的三口烧瓶中，恒压漏斗中装有15g的甲基苯基二甲氧基硅氧烷，在80℃的油浴，600rpm转速的机械搅拌中缓慢滴加甲基苯基二甲氧基硅氧烷，待甲基苯基二甲氧基硅氧烷滴加完毕后，再滴加约1.5g的蒸馏水，反应5h后即得到第一步改性产物。在第一步改性产物的基础上，在70℃的油浴，600rpm转速搅拌中继续滴加15g的含氢硅油，在500ppm的Karstedt催化剂催化下反应60min后即得到有机硅改性环氧树脂。According to the proportioning of reactant, the dibutyltin dilaurate of 100g two parts of A-type epoxy resin E51 and 1g is placed in the there-necked flask that condensation reflux and constant pressure dropping funnel are housed, and 15g of dibutyltin dilaurate is housed in the constant pressure funnel. Methylphenyldimethoxysiloxane, in an oil bath at 80°C, slowly add methylphenyldimethoxysiloxane dropwise in an oil bath at 600rpm, until methylphenyldimethoxysiloxane After the dropwise addition of the oxane was completed, about 1.5 g of distilled water was added dropwise, and the modified product of the first step was obtained after 5 hours of reaction. On the basis of the modified product in the first step, continue to drop 15g of hydrogen-containing silicone oil in an oil bath at 70°C and stir at 600rpm, and react for 60min under the catalysis of 500ppm Karstedt catalyst to obtain a silicone-modified epoxy resin .
实施例2-4所得的最终产物与未改性的环氧树脂的红外光谱对比如图相似；实施例2-4所得产物的差式扫描量热分析曲线(DSC)曲线与图2相似，不一一提供。The infrared spectrum comparison of the final product of embodiment 2-4 gained and unmodified epoxy resin is similar to the figure; The differential scanning calorimetry curve (DSC) curve of embodiment 2-4 gained product is similar to Fig. 2, not Offer them one by one.
本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The implementation of the present invention is not limited by the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods, including Within the protection scope of the present invention.
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