TWI771285B - Aromatic polyamide surface modifier for silica sol - Google Patents

Aromatic polyamide surface modifier for silica sol Download PDF

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TWI771285B
TWI771285B TW106103326A TW106103326A TWI771285B TW I771285 B TWI771285 B TW I771285B TW 106103326 A TW106103326 A TW 106103326A TW 106103326 A TW106103326 A TW 106103326A TW I771285 B TWI771285 B TW I771285B
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aromatic polyamide
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橫澤勉
江原和也
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日商日產化學工業股份有限公司
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Abstract

一種具有式(1)所表示之特徵的芳香族聚醯胺，其可被利用作為無機微粒子表面之修飾劑。 An aromatic polyamide having the characteristics represented by the formula (1), which can be used as a modifier on the surface of inorganic fine particles.

Figure 106103326-A0202-11-0001-1
(式中，X表示碳數1~10之伸烷基，R’表示彼此獨立的碳數1~10之烷基或碳數6~20之芳基，R1以及R2表示彼此獨立的碳數1~10之烷基，R3表示彼此獨立的碳數1~10之烷基或碳數6~20之芳基，n表示2以上之整數，k表示1~3之整數)。
Figure 106103326-A0202-11-0001-1
 (in the formula, X represents an alkyl group with 1 to 10 carbon atoms, R' represents an alkyl group with 1 to 10 carbon atoms or an aryl group with 6 to 20 carbon atoms, and R 1 and R 2 represent independent carbon atoms. An alkyl group of 1 to 10, R 3 represents an alkyl group of 1 to 10 carbon atoms or an aryl group of 6 to 20 carbon atoms independently of each other, n represents an integer of 2 or more, and k represents an integer of 1 to 3).

Description

矽溶膠的芳香族聚醯胺表面修飾劑 Aromatic polyamide surface modifier for silica sol

本發明是關於一種芳香族聚醯胺，更詳細的說，是關於一種可被利用作為無機微粒子的表面修飾等之芳香族聚醯胺。 The present invention relates to an aromatic polyamide, more specifically, an aromatic polyamide that can be used as surface modification of inorganic fine particles.

以往，為了提升有機材料之耐熱性、力學特性以及電氣特性，有關將矽溶膠或氧化鈦等無機微粒子與有機高分子混合而得之混合材料(奈米複合材料)常被充分進行研究。 In the past, in order to improve the heat resistance, mechanical properties, and electrical properties of organic materials, hybrid materials (nanocomposites) obtained by mixing inorganic fine particles such as silica sol or titanium oxide with organic polymers have been extensively studied.

但，有機材料與無機材料之性質原先就具很大差異，加上可添加之無機微粒子的量受到限制等問題，不僅添加之無機微粒子不易分散於有機材料中，尚存在添加之無機微粒子隨著時間而於有機材料中產生凝聚等問題。 However, the properties of organic materials and inorganic materials are very different from the beginning, and the amount of inorganic fine particles that can be added is limited. Problems such as agglomeration occur in organic materials over time.

因此，為了解決這些問題，已有開始利用有機低分子化合物或有機高分子對無機微粒子表面進行修飾。 Therefore, in order to solve these problems, the surfaces of inorganic fine particles have been modified with organic low molecular weight compounds or organic polymers.

特別是在使用有機高分子進行修飾的情形，主要有(1)將起始部位導入無機表面後，再由該處進行活性聚 合，或(2)在活性聚合物末端導入可與無機物鍵結之官能基(-Si(OR)3，-PO3H，-CO2H，-SH等)，使其與無機微粒子表面進行反應，等兩種方法。 Especially in the case of using organic polymers for modification, there are mainly (1) introduction of the starting site into the inorganic surface, and then living polymerization from there, or (2) introduction of a polymer that can bond with inorganic substances at the end of the living polymer. Functional groups (-Si(OR) 3 , -PO 3 H, -CO 2 H, -SH, etc.) to react with the surface of inorganic fine particles, and the like.

但活性聚合僅限於加成聚合與開環聚合，故所得之聚合物為不具耐熱性的脂肪族聚合物。在該情形下，即便將無機微粒子混入有機材料中欲提升其耐熱性時，經表面修飾之脂肪族聚合物會先被熱分解，故會存在與混合無表面修飾之無機微粒子的材料為相同的問題。又，修飾過的脂肪族聚合物不易與高耐熱性之縮合系芳香族聚合物混合也是一大問題。 However, living polymerization is limited to addition polymerization and ring-opening polymerization, so the resulting polymer is an aliphatic polymer without heat resistance. In this case, even if the inorganic microparticles are mixed into the organic material to improve the heat resistance, the surface-modified aliphatic polymer will be thermally decomposed first, so there will be the same material as the material mixed with the inorganic microparticles without surface modification. question. In addition, it is also a problem that the modified aliphatic polymer is not easily mixed with the condensed aromatic polymer having high heat resistance.

欲解決這些問題時，可用具有優良耐熱性之縮合系芳香族高分子來修飾無微粒子表面即可。但是縮合系芳香族高分子僅能由縮聚合法產生，而無法活用到活性聚合特性之上述(1)及(2)之方式。 To solve these problems, the surface without fine particles may be modified with a condensed aromatic polymer having excellent heat resistance. However, the condensed aromatic polymer can be produced only by the condensation polymerization method, and the above-mentioned (1) and (2) of the living polymerization characteristics cannot be utilized.

[先行技術文獻] [Prior Technology Literature] [非專利文獻] [Non-patent literature]

[非專利文獻1] J. Am. Chem. Soc. 122, 8313 (2000) [Non-Patent Document 1] J. Am. Chem. Soc. 122, 8313 (2000)

本發明即是鑑於該些情形而提出者，而以提供一種可被利用作為無機微粒子之表面修飾的芳香族聚醯 胺為目的。 The present invention is made in view of these circumstances, and provides an aromatic polyamide that can be used as a surface modification of inorganic fine particles amine for the purpose.

本發明者們，利用先前研究之縮聚合法的活性聚合之鏈成長縮聚合法(CGCP)之芳香族聚醯胺聚合法(參考非專利文獻1)中，使用具有不飽和鍵之引發劑得到之不飽和末端，而導入可與無機物表面反應的Si(OR)3等之結果，發現可被利用作為無機微粒子表面的修飾劑之芳香族聚醯胺，因而完成本發明。 The inventors of the present invention have obtained an unsaturated bond using an initiator having an unsaturated bond in an aromatic polyamide polymerization method (refer to Non-Patent Document 1), which is a chain-growth polycondensation method (CGCP) of living polymerization using a polycondensation method previously studied. As a result of introducing Si(OR) 3 which can react with the surface of inorganic substances by introducing a saturated terminal, etc., aromatic polyamides which can be used as modifiers on the surface of inorganic fine particles have been found, and the present invention has been completed.

即，本發明為 That is, the present invention is

1.一種芳香族聚醯胺，其特徵為，如式(1)所表示者，

Figure 106103326-A0202-12-0003-2
(式中，X表示碳數1~10之伸烷基，R’表示彼此獨立的碳數1~10之烷基或碳數6~20之芳基，R1以及R2表示彼此獨立的碳數1~10之烷基，R3表示彼此獨立的碳數1~10之烷基或碳數6~20之芳基，n表示2以上之整數，k表示1~3之整數)。 1. An aromatic polyamide, characterized in that, as represented by formula (1),
Figure 106103326-A0202-12-0003-2
 (in the formula, X represents an alkyl group with 1 to 10 carbon atoms, R' represents an alkyl group with 1 to 10 carbon atoms or an aryl group with 6 to 20 carbon atoms, and R 1 and R 2 represent independent carbon atoms. An alkyl group of 1 to 10, R 3 represents an alkyl group of 1 to 10 carbon atoms or an aryl group of 6 to 20 carbon atoms independently of each other, n represents an integer of 2 or more, and k represents an integer of 1 to 3).

2.如1之芳香族聚醯胺，其為式(2)所表示者，

Figure 106103326-A0202-12-0004-3
(式中，R’、R1、R2以及n與前述相同)。 2. The aromatic polyamide of 1, which is represented by the formula (2),
Figure 106103326-A0202-12-0004-3
 (In the formula, R', R 1 , R 2 and n are the same as described above).

3.一種芳香族聚醯胺，其特徵為，如式(3)所表示者，

Figure 106103326-A0202-12-0004-4
(式中，R表示含有不飽和鍵結之基，R1以及R2表示彼此獨立的碳數1~10之烷基，n表示2以上之整數)。 3. An aromatic polyamide, characterized in that, as represented by formula (3),
Figure 106103326-A0202-12-0004-4
 (In the formula, R represents a group containing an unsaturated bond, R 1 and R 2 represent independently an alkyl group having 1 to 10 carbon atoms, and n represents an integer of 2 or more).

4.如3之芳香族聚醯胺，其為式(4)所表示者，

Figure 106103326-A0202-12-0004-6
(式中，R1、R2以及n與前述相同)。 4. The aromatic polyamide of 3, which is represented by the formula (4),
Figure 106103326-A0202-12-0004-6
 (In the formula, R 1 , R 2 and n are the same as described above).

5.如1~4中任1項之芳香族聚醯胺，其中，前述R1以及R2表示彼此獨立的甲基或乙基。 5. The aromatic polyamide according to any one of 1 to 4, wherein the aforementioned R 1 and R 2 represent independently methyl groups or ethyl groups.

6.一種無機微粒子，其特徵為，經1~5中任1項之芳香族聚醯胺表面修飾者。 6. An inorganic microparticle characterized by being surface-modified with an aromatic polyamide according to any one of 1 to 5.

7.一種有機．無機混合材料，其特徵為，含有6之無機微粒子與有機基體樹脂。 7. An organic. The inorganic hybrid material is characterized by containing 6 inorganic fine particles and an organic matrix resin.

8.一種薄膜，其特徵為，使用7之有機．無機混合材料所製得者。 8. A film, characterized in that the use of 7 organic. Made of inorganic mixed materials.

依本發明之內容，可提供一種可被利用作為無機粒子表面的修飾劑之芳香族聚醯胺。 According to the content of the present invention, an aromatic polyamide that can be used as a modifier on the surface of inorganic particles can be provided.

可期待利用此芳香族聚醯胺修飾矽或氮化硼等的無機微粒子表面，與聚醯伸胺等耐熱性高分子混合後，可開發出進一步提高耐熱性及力學特性之有機．無機混合材料。 It is expected to use this aromatic polyamide to modify the surface of inorganic fine particles such as silicon and boron nitride, and to mix it with heat-resistant polymers such as polyamide to develop organic compounds that further improve heat resistance and mechanical properties. Inorganic hybrid materials.

[發明之實施型態] [implementation form of the invention]

以下就本發明做更詳細之說明。 The present invention will be described in more detail below.

本發明之芳香族聚醯胺，係如下述式(1)所表示者。 The aromatic polyamide of the present invention is represented by the following formula (1).

Figure 106103326-A0202-12-0005-7
Figure 106103326-A0202-12-0005-7

式(1)中，X表示碳數1~10之伸烷基，R’表示彼此獨立的碳數1~10之烷基或碳數6~20之芳基，R1以及R2表示彼此獨立的碳數1~10之烷基，R3表示彼此獨立的碳數1~10之烷基或碳數6~20之芳基，n表示2以上之整數，k表示1~3之整數。 In the formula (1), X represents an alkylene group with 1 to 10 carbon atoms, R' represents an alkyl group with 1 to 10 carbon atoms or an aryl group with 6 to 20 carbon atoms, which are independent of each other, and R 1 and R 2 are independent of each other. The alkyl group of carbon number 1-10, R 3 represents the alkyl group of carbon number 1-10 or the aryl group of carbon number 6-20 independently of each other, n represents an integer of 2 or more, and k represents an integer of 1-3.

碳數1~10之伸烷基的具體例，可列舉如，伸甲基、伸乙基、甲基伸乙基、伸三甲基、伸丙基、甲基伸丙基、伸四甲基、伸五甲基、伸六甲基、伸七甲基、伸八甲基、伸十甲基等，其中，以碳數1~5之伸烷基為佳，較佳為碳數1~3之伸烷基，更佳為伸三甲基。 Specific examples of alkylene groups having 1 to 10 carbon atoms include methylidene, ethylidene, methylethylidene, trimethylidene, propylidene, methylenepropylidene, tetramethylidene, Pentamethyl, hexamethyl, heptamethyl, octamethyl, decamethyl, etc., wherein, the alkylene with carbon number 1~5 is preferably, preferably the carbon number 1~3 alkylene, more preferably trimethyl.

碳數1~10之烷基的具體例，可列舉如，甲基、乙基、正丙基、異丙基、環丙基、正丁基、異丁基、仲丁基、叔丁基、正戊基、1-甲基-正丁基、2-甲基-正丁基、3-甲基-正丁基、1,1-二甲基-正丙基、1,2-二甲基-正丙基、2,2-二甲基-正丙基、1-乙基-正丙基、環戊基、正己基、1-甲基-正戊基、2-甲基-正戊基、3-甲基-正戊基、4-甲基-正戊基、1,1-二甲基-正丁基、1,2-二甲基-正丁基、1,3-二甲基-正丁基、2,2-二甲基-正丁基、2,3-二甲基-正丁基、3,3-二甲基-正丁基、1-乙基-正丁基、2-乙基-正丁基、1,1,2-三甲基-正丙基、1,2,2-三甲基-正丙基、1-乙基-1-甲基-正丙基、1-乙基-2-甲基-正丙基、環己基、正庚基、正辛基、正壬基、正癸基等。 Specific examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl - n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl , 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl -n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl, 1-ethyl-n-butyl, 2-Ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl , 1-ethyl-2-methyl-n-propyl, cyclohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, etc.

碳數6~20之芳基的具體例，可列舉如，苯基、α-萘基、β-萘基，鄰聯苯基、間聯苯基、對聯苯基、1-蒽基、2-蒽基、9-蒽基、1-菲基、2-菲基、3-菲基、4-菲基、9-菲基等。 Specific examples of the aryl group having 6 to 20 carbon atoms include phenyl, α-naphthyl, β-naphthyl, o-biphenyl, m-biphenyl, p-biphenyl, 1-anthryl, 2- Anthracenyl, 9-anthracenyl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, etc.

其中，R’、R1、R2，以甲基、乙基為佳，又，R3以碳數1~8之烷基為佳，較佳為碳數1~5之烷基，更佳為甲基、乙基、正丙基、異丙基、正丁基、正戊基、正辛基。 Among them, R', R 1 , R 2 are preferably methyl and ethyl, and R 3 is preferably an alkyl group with 1 to 8 carbon atoms, preferably an alkyl group with 1 to 5 carbon atoms, more preferably For methyl, ethyl, n-propyl, isopropyl, n-butyl, n-pentyl, n-octyl.

k表示1~3之整數，又以2或3為佳，以3為更佳。 k represents an integer from 1 to 3, preferably 2 or 3, more preferably 3.

n為2以上之整數時，則無特別限制，但以2~100的整數為佳。 When n is an integer of 2 or more, there is no particular limitation, but an integer of 2 to 100 is preferable.

上述(1)所示之芳香族聚醯胺中，以下述式(2)所表示者為佳。 Among the aromatic polyamides represented by the above (1), those represented by the following formula (2) are preferred.

Figure 106103326-A0202-12-0007-8
Figure 106103326-A0202-12-0007-8

以上說明之芳香族聚醯胺，可將上述非專利文獻1的方法而得之下述式(3)所示的芳香族聚醯胺作為原料而製得。 The aromatic polyamide described above can be produced by using, as a raw material, an aromatic polyamide represented by the following formula (3) obtained by the method of the above-mentioned Non-Patent Document 1.

Figure 106103326-A0202-12-0007-9
Figure 106103326-A0202-12-0007-9

於式(3)之中，R表示含有不飽和鍵結之基，R1、R2、n與上述意義相同。 In formula (3), R represents a group containing an unsaturated bond, and R 1 , R 2 and n have the same meanings as described above.

含有不飽和鍵結之基，雖無特別限定之內容，但考慮到隨後與硫醇的自由基加成反應效率時，以乙烯基、烯丙基、高烯丙基等具有末端雙鍵者為佳，此情況雖配合R而 會產生具有各種間隔之芳香族聚醯胺，但欲製得上述式(1)所表示之芳香族聚醯胺，必須使用下述式(4)表示之R為烯丙基的芳香族聚醯胺。 The group containing unsaturated bond is not particularly limited, but when considering the efficiency of the subsequent radical addition reaction with thiol, vinyl, allyl, homoallyl, etc. with terminal double bonds are good, although this situation is compatible with R Aromatic polyamides with various gaps are produced, but in order to obtain the aromatic polyamides represented by the above formula (1), it is necessary to use the aromatic polyamides represented by the following formula (4) where R is an allyl group amine.

Figure 106103326-A0202-12-0008-10
(式中，R1、R2以及n與前述相同)。
Figure 106103326-A0202-12-0008-10
 (In the formula, R 1 , R 2 and n are the same as described above).

將上述式(4)所示的具有烯丙基之芳香族聚醯胺，與含有烷氧基矽烷基之硫醇化合物進行自由基加成反應，即可製得式(1)所示之芳香族聚醯胺。 The aromatic polyamide represented by the formula (1) can be prepared by performing a radical addition reaction with the aromatic polyamide having an allyl group represented by the above formula (4) and a thiol compound containing an alkoxysilyl group Polyamides.

該情形下，式(4)之芳香族聚醯胺與具有烷氧基矽烷基之硫醇化合物的反應比率，並無特別限制，但考慮反應速率等時，相對於式(4)之芳香族聚醯胺1mol，硫醇化合物可使用1~100mol的程度，又以5~50mol為佳，以10~30mol為更佳。 In this case, the reaction ratio of the aromatic polyamide of the formula (4) and the thiol compound having an alkoxysilyl group is not particularly limited, but considering the reaction rate and the like, the ratio of the aromatic polyamide of the formula (4) to the For 1 mol of polyamide, the thiol compound can be used in the range of 1 to 100 mol, preferably 5 to 50 mol, and more preferably 10 to 30 mol.

具有烷氧基矽烷基之硫醇化合物的具體例，可列舉如，3-(三甲氧基矽烷基)丙烷硫醇、3-(三乙氧基矽烷基)丙烷硫醇等。 Specific examples of the thiol compound having an alkoxysilyl group include 3-(trimethoxysilyl)propanethiol, 3-(triethoxysilyl)propanethiol, and the like.

聚合引發劑，只要可被熱或還原性物質分解而產生自由基者，並無特別之限制，例如，2,2’-偶氮二異丁腈等偶氮化合物；過氧化苯甲醯、過苯甲酸叔丁酯、叔丁基氫過氧化物、二叔丁基過氧化物、過氧化氫異丙苯等過氧化物，這些可被單獨使用，也可將兩種以上組合使 用。 Polymerization initiators are not particularly limited as long as they can be decomposed by heat or reducing substances to generate free radicals, for example, azo compounds such as 2,2'-azobisisobutyronitrile; Peroxides such as tert-butyl benzoate, tert-butyl hydroperoxide, di-tert-butyl peroxide, cumene hydroperoxide, etc. can be used alone or in combination of two or more. use.

上述反應也可在有機溶劑中進行。 The above reaction can also be carried out in an organic solvent.

此反應所使用之溶劑，只要可溶解芳香族聚醯胺，不會妨礙聚合反應者皆可任意使用，例如，戊烷、己烷、庚烷、辛烷、環己烷等脂族烴類；***、二異丙醚、二丁醚、環戊基甲醚、四氫呋喃、1,4-二噁烷等醚類；苯、甲苯、二甲苯、均三甲苯、茴香醚等芳香烴類；氯仿、二氯甲烷、二氯乙烷、四氯化碳等鹵代烴類；乙腈、丙腈等腈類，其中，又以腈類為佳，較佳為乙腈。 The solvent used in this reaction can be arbitrarily used as long as it can dissolve the aromatic polyamide and will not hinder the polymerization reaction, for example, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, and cyclohexane; Diethyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, tetrahydrofuran, 1,4-dioxane and other ethers; benzene, toluene, xylene, mesitylene, anisole and other aromatic hydrocarbons; chloroform, Halogenated hydrocarbons such as dichloromethane, dichloroethane and carbon tetrachloride; nitriles such as acetonitrile and propionitrile, among which nitriles are preferred, and acetonitrile is preferred.

反應溫度以50~150℃左右為佳，較佳為60~100℃左右。 The reaction temperature is preferably about 50 to 150°C, preferably about 60 to 100°C.

反應時間，一般為1~120小時左右。 The reaction time is generally about 1 to 120 hours.

反應結束後，可依一般流程做後處理，可配合必要性等，予以再沈澱等純化處理，而得到目的物。 After the completion of the reaction, post-treatment can be performed according to the general procedure, and the target compound can be obtained by performing purification treatment such as reprecipitation according to necessity.

所製得的式(1)所示之芳香族聚醯胺，因其末端帶有烷氧基，故可利用此烷氧矽烷基對無機微粒子的表面或無機基板的表面進行修飾。 The obtained aromatic polyamide represented by the formula (1) has an alkoxy group at the terminal, so the surface of the inorganic fine particle or the surface of the inorganic substrate can be modified with the alkoxysilyl group.

因芳香族聚醯胺具有良好的耐熱性，故將本發明之芳香族聚醯胺作為無機材料之表面處理劑使用的同時，並使用聚醯伸胺、聚醯胺等具有良好耐熱性的樹脂作為有機基體時，可期待開發出具有良好耐熱性以及力學特性的有機、無機混合材料。 Since aromatic polyamides have good heat resistance, the aromatic polyamides of the present invention are used as surface treatment agents for inorganic materials, and resins with good heat resistance such as polyamides and polyamides are used. As an organic matrix, the development of organic-inorganic hybrid materials with good heat resistance and mechanical properties can be expected.

[實施例] [Example]

以下，將列舉實施例，具體的說明本發明，但本發明並不受下述實施例所限制。實施例所使用之各量測裝置如以下。 Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited by the following examples. The measurement devices used in the examples are as follows.

[GPC] [GPC] (1)Poly1，Poly2 (1) Poly1, Poly2

裝置：Shodex GPC-101(昭和電工(股)製) Device: Shodex GPC-101 (manufactured by Showa Denko Co., Ltd.)

管柱：Shodex KF-804L 2柱(昭和電工(股)製) Column: Shodex KF-804L 2-column (manufactured by Showa Denko Co., Ltd.)

管柱溫度：40℃ Column temperature: 40℃

溶劑：四氫呋喃1mL/分鐘 Solvent: Tetrahydrofuran 1mL/min

檢測器：UV(254nm)、RI Detector: UV (254nm), RI

校準曲線：標準聚苯乙烯 Calibration Curve: Standard Polystyrene

(2)聚醯胺酸S1 (2) Polyamide S1

裝置：Shodex GPC-101(昭和電工(股)製) Device: Shodex GPC-101 (manufactured by Showa Denko Co., Ltd.)

管柱：Shodex KD801以及KD805(昭和電工(股)製) Column: Shodex KD801 and KD805 (manufactured by Showa Denko Co., Ltd.)

管柱溫度：40℃ Column temperature: 40℃

溶劑：二甲基甲醯胺/LiBr．H2O(29.6mM)/H3PO4(29.6mM)/ Solvent: dimethylformamide/LiBr. H 2 O (29.6 mM)/H 3 PO 4 (29.6 mM)/

檢測器：UV(254nm)、RI Detector: UV (254nm), RI

校準曲線：標準聚氧化乙烯 Calibration curve: standard polyethylene oxide

[1H-NMR] [ 1 H-NMR]

裝置：JEOL ECA-500 and ECA-600 Installation: JEOL ECA-500 and ECA-600

[TG-DTA] [TG-DTA]

裝置：Seiko Instruments Inc.TG/DTA 6200 Device: Seiko Instruments Inc.TG/DTA 6200

[實施例1]Poly1之製造 [Example 1] Manufacturing of Poly1

Figure 106103326-A0202-12-0011-12
Figure 106103326-A0202-12-0011-12

將100mL茄型燒瓶於減壓下，使用熱槍加熱後，經氬氣取代並冷卻至室溫。進一步冷卻至-10℃，在氮氣流下加入1MLiHMDS的THF溶液11mL(11.0mmol)，並在氮氣流下加入溶解於乾燥THF5.2mL之4-烯丙氧基甲基苯甲酸(1)0.21g(1.11mmol)。隨後，立即以40分鐘將溶解於乾燥THF13.0mL之3-(乙基氨基)苯甲酸乙酯(2)2.04g(10.54mmol)滴入其中，其後再於-10℃下攪拌。6分鐘後抽樣觀察反應過程，並在2小時後用飽和氯化銨水溶液停止聚合。以二氯甲烷萃取後，使用水洗淨3次，並使用無水硫酸鎂乾燥。於減壓下將溶劑餾除，所得之粗製品使用作為良溶劑之氯仿、作為貧溶劑之***進行沈澱純化，而製得黃色固體產量1.30克(產率70%)(Mn=2500，Mw/Mn=1.23，平均聚合度=20.2)。 A 100 mL eggplant-shaped flask was heated with a heat gun under reduced pressure, replaced with argon, and cooled to room temperature. It was further cooled to -10°C, 11 mL (11.0 mmol) of a 1M LiHMDS solution in THF was added under nitrogen flow, and 0.21 g (1.11 g) of 4-allyloxymethylbenzoic acid (1) dissolved in 5.2 mL of dry THF was added under nitrogen flow. mmol). Then, 2.04 g (10.54 mmol) of ethyl 3-(ethylamino)benzoate (2) dissolved in 13.0 mL of dry THF was immediately added dropwise thereto over 40 minutes, followed by stirring at -10°C. After 6 minutes, sampling was performed to observe the reaction progress, and the polymerization was stopped after 2 hours with saturated aqueous ammonium chloride solution. After extraction with dichloromethane, it was washed three times with water and dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure, and the obtained crude product was purified by precipitation using chloroform as a good solvent and diethyl ether as a poor solvent to obtain a yellow solid yield of 1.30 g (yield 70%) (Mn=2500, Mw/ Mn=1.23, average degree of polymerization=20.2).

[實施例2]Poly2之製造 [Example 2] Manufacturing of Poly2

Figure 106103326-A0202-12-0012-13
Figure 106103326-A0202-12-0012-13

於20mL壓力反應管中，加入無水乙腈14.70mL、Poly 1 0.70g(0.22mmol)、3-(三甲氧基矽烷基)丙烷硫醇2.99mL(15.40mmol)以及2,2’-偶氮二異丁腈18.50mg(0.11mmol)。使用液態氮冷凍後，將反應容器內部減壓、密閉後回到室溫，使溶劑中的溶解氣體發泡。重複此一連串操作(凍結脫氣)5次後，於在80℃下攪拌12小時。將溶劑餾除後，所得之產物使用作為良溶劑之氯仿，作為貧溶劑之正己烷：二噁烷=10：1(v/v)的混合溶液進行沈澱純化，而製得黃白色固體產量0.52g(產率70%)。 In a 20mL pressure reaction tube, add 14.70mL of anhydrous acetonitrile, 0.70g (0.22mmol) of Poly 1, 2.99mL (15.40mmol) of 3-(trimethoxysilyl)propanethiol and 2,2'-azodiiso Butyronitrile 18.50 mg (0.11 mmol). After freezing with liquid nitrogen, the inside of the reaction vessel was decompressed and airtight, and then returned to room temperature to foam the dissolved gas in the solvent. After repeating this series of operations (freezing and degassing) 5 times, the mixture was stirred at 80°C for 12 hours. After the solvent was distilled off, the obtained product was purified by precipitation using chloroform as a good solvent, and a mixed solution of n-hexane:dioxane=10:1 (v/v) as a poor solvent to obtain a yellow-white solid yield of 0.52 g (70% yield).

[實施例3]矽溶膠之合成 [Example 3] Synthesis of silica sol

於壓力反應管中，加入實施例2所製得之Poly2(Mn=2100，Mw/Mn=1.18、平均聚合度=15)0.0878g(0.03mmol)、DMAc1.0g，於室溫攪拌後，加入DMAc-矽溶膠溶液0.64g(矽含量：0.128g)，於50℃下攪拌，12小時後將反應停止。將反應後之溶劑於減壓下餾除，於所得之產物中加入氯仿，進行傾析，使其分為可溶部(30%)與不溶部(70%)。將可溶部濃縮後，分別將所 得到之產物減壓乾燥。 In a pressure reaction tube, add Poly2 (Mn=2100, Mw/Mn=1.18, average degree of polymerization=15) 0.0878 g (0.03 mmol) and 1.0 g of DMAc prepared in Example 2, and after stirring at room temperature, add 0.64 g of DMAc-silica sol solution (silicon content: 0.128 g) was stirred at 50° C., and the reaction was stopped after 12 hours. The solvent after the reaction was distilled off under reduced pressure, and chloroform was added to the obtained product, followed by decantation, so that it was divided into a soluble part (30%) and an insoluble part (70%). After concentrating the soluble part, the The obtained product was dried under reduced pressure.

將可溶部之一部分進行質量測定同時進行抽樣，並加入對苯二甲醛做為內部標準物質，從1H-NMR譜計算出三甲氧基矽烷基之轉化率結果，其轉化率為99%。又，於測定可溶部和不溶部的TG-DTA結果，從重量減少率計算出矽中之聚醯胺的比例。得知可溶部為84%、不溶部為22%。又，為了使固體含量達10%，將可溶部再溶解於DMAc。 A part of the soluble part was sampled for mass measurement, and terephthalaldehyde was added as an internal standard material. The conversion rate of trimethoxysilyl group was calculated from the 1 H-NMR spectrum, and the conversion rate was 99%. In addition, the ratio of polyamide in silicon was calculated from the weight loss rate in the measurement of TG-DTA results of the soluble part and the insoluble part. It was found that the soluble part was 84% and the insoluble part was 22%. Moreover, in order to make solid content 10%, the soluble part was redissolved in DMAc.

[實施例4]混合薄膜之製作 [Example 4] Production of hybrid film (1)聚醯胺酸(S1)的合成 (1) Synthesis of Polyamide (S1)

將對苯二胺3.218g(30mmol)溶解於DMAc88.2g中。於製得的溶液中加入3,3’,4,4’-聯苯四羧酸二酐8.581g(29mmol)，於氮氣氛圍中，於23℃下反應24小時。所得之聚醯胺酸的Mw為107,300、分子量分佈為4.6。 3.218 g (30 mmol) of p-phenylenediamine were dissolved in 88.2 g of DMAc. To the obtained solution, 8.581 g (29 mmol) of 3,3',4,4'-biphenyltetracarboxylic dianhydride was added, and the reaction was carried out at 23°C for 24 hours in a nitrogen atmosphere. The Mw of the obtained polyamic acid was 107,300, and the molecular weight distribution was 4.6.

(2)混合薄膜之製作 (2) Production of mixed film

於上述製得之聚醯胺酸6.0g中，添加實施例3製得之矽溶膠溶液(可溶部)0.90g，於23℃下攪拌3小時而製得塗劑。其後，使用條狀塗佈機於玻璃基板上塗上此塗劑，製得膜厚度250μm的塗膜，隨後進行80℃、1小時、300℃、1小時之燒製。 To 6.0 g of the polyamic acid obtained above, 0.90 g of the silica sol solution (soluble part) obtained in Example 3 was added, and the mixture was stirred at 23° C. for 3 hours to prepare a coating agent. Then, the coating agent was applied on a glass substrate using a strip coater to obtain a coating film with a film thickness of 250 μm, followed by firing at 80° C., 1 hour, 300° C., and 1 hour.

所製得之薄膜未出現白濁現象，為漂亮的黃色薄膜。 又，將此薄膜使用刀具從玻璃基板上剝離時，可輕易的剝離。觀察出剝離之薄膜具有強大的自我支撐性。 The obtained film did not appear cloudy and was a beautiful yellow film. Moreover, when this film is peeled off from a glass substrate using a knife, it can peel easily. The peeled films were observed to be strongly self-supporting.

[實施例5]混合薄膜之製作 [Example 5] Production of hybrid film

於上述製得之聚醯胺酸1.0g中，添加實施例3製得之矽溶膠溶液(可溶部)1.50g，於23℃下攪拌3小時而製得塗劑。其後，使用條狀塗佈機於玻璃基板上塗上此塗劑，製得膜厚度250μm的塗膜，隨後進行80℃、1小時、300℃、1小時之燒製。 To 1.0 g of the polyamic acid obtained above, 1.50 g of the silica sol solution (soluble portion) obtained in Example 3 was added, and the mixture was stirred at 23° C. for 3 hours to prepare a coating agent. Then, the coating agent was applied on a glass substrate using a strip coater to obtain a coating film with a film thickness of 250 μm, followed by firing at 80° C., 1 hour, 300° C., and 1 hour.

所製得之薄膜未出現白濁，為漂亮的黃色薄膜。又，將此薄膜使用刀具從玻璃基板上剝離時，可輕易的剝離。觀察出剝離之薄膜具有強大的自我支撐性。 The obtained film did not appear cloudy and was a beautiful yellow film. Moreover, when this film is peeled off from a glass substrate using a knife, it can peel easily. The peeled films were observed to be strongly self-supporting.

Claims (6)

一種芳香族聚醯胺，其特徵為，如式(1)所表示者；
Figure 106103326-A0305-02-0017-1
 (式中，X表示碳數1~10之伸烷基，R’表示彼此獨立的碳數1~10之烷基或碳數6~20之芳基，R1以及R2表示彼此獨立的碳數1~10之烷基，R3表示彼此獨立的碳數1~10之烷基或碳數6~20之芳基，n表示2以上之整數，k表示1~3之整數)。 An aromatic polyamide, characterized by being represented by formula (1);
Figure 106103326-A0305-02-0017-1
 (in the formula, X represents an alkyl group with 1 to 10 carbon atoms, R' represents an alkyl group with 1 to 10 carbon atoms or an aryl group with 6 to 20 carbon atoms, and R 1 and R 2 represent independent carbon atoms. An alkyl group of 1 to 10, R 3 represents an alkyl group of 1 to 10 carbon atoms or an aryl group of 6 to 20 carbon atoms independently of each other, n represents an integer of 2 or more, and k represents an integer of 1 to 3). 如請求項1之芳香族聚醯胺，其為式(2)所表示者；
Figure 106103326-A0305-02-0017-2
 (式中，R’、R1、R2以及n與請求項1內容相同)。 The aromatic polyamide of claim 1, which is represented by formula (2);
Figure 106103326-A0305-02-0017-2
 (In the formula, R', R 1 , R 2 and n are the same as in claim 1). 如請求項1或2之芳香族聚醯胺，其中，前述R1以及R2表示彼此獨立的甲基或乙基。 The aromatic polyamide according to claim 1 or 2, wherein the aforementioned R 1 and R 2 represent independently methyl or ethyl groups. 一種無機微粒子，其特徵為，經請求項1~3中任1項之芳香族聚醯胺表面修飾者。 An inorganic microparticle characterized by being surface-modified with an aromatic polyamide according to any one of Claims 1 to 3. 一種有機‧無機混合材料，其特徵為，含有請求項4之無機微粒子與有機基體樹脂。 An organic-inorganic hybrid material characterized by containing the inorganic fine particles of claim 4 and an organic matrix resin. 一種薄膜，其特徵為，使用請求項5之有機‧無機混合材料所製得者。 A thin film produced by using the organic-inorganic hybrid material of claim 5.
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