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TWI833458B - Dual curable epoxy-terminated polysiloxane and preparation method and application thereof - Google Patents

Dual curable epoxy-terminated polysiloxane and preparation method and application thereof Download PDF

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TWI833458B
TWI833458B TW111144429A TW111144429A TWI833458B TW I833458 B TWI833458 B TW I833458B TW 111144429 A TW111144429 A TW 111144429A TW 111144429 A TW111144429 A TW 111144429A TW I833458 B TWI833458 B TW I833458B
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epoxy
polysiloxane
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TW202421695A (en
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黃宇劍
卓勝池
徐悅
何錄紅
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長興材料工業股份有限公司
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Abstract

A dual curable epoxy-terminated polysiloxane and preparation method and application thereof are provided. Specifically, an epoxy-terminated polysiloxane is provided. The epoxy-terminated polysiloxane has multiple cross-linking groups, has good adhesion, and is useful in various fields. The epoxy-terminated polysiloxane can be prepared easily and efficiently.

Description

可雙固化的端環氧基聚矽氧烷及其製備方法與應用Dual-curable epoxy-terminated polysiloxane and its preparation method and application

本發明屬於環氧有機聚矽氧烷領域,具體地,本發明涉及一種可雙固化的端環氧基聚矽氧烷及其製備方法。 The present invention belongs to the field of epoxy organopolysiloxane. Specifically, the present invention relates to a dual-curable terminal epoxy polysiloxane and a preparation method thereof.

環氧樹脂是一種高分子聚合物,是指分子中含有二個以上環氧基團的一類聚合物的總稱。組成中含有較多環氧基團的塗料統稱為環氧漆。環氧樹脂是一種重要的熱固性樹脂。純環氧樹脂在固化後,化學交聯密度高、分子鏈柔順性低、內應力大,導致環氧樹脂固化物脆性較高,耐衝擊性和抗疲勞耐久性較差,因此其應用範圍受到了限制。 Epoxy resin is a kind of high molecular polymer, which refers to the general name of a class of polymers containing more than two epoxy groups in the molecule. Coatings containing more epoxy groups in their composition are collectively called epoxy paints. Epoxy resin is an important thermosetting resin. After curing, pure epoxy resin has high chemical cross-linking density, low molecular chain flexibility, and large internal stress, resulting in high brittleness of the cured epoxy resin and poor impact resistance and fatigue resistance durability. Therefore, its application scope has been limited. limit.

鑒於此,亟需找到一種力學強度高、有韌性、耐高低溫的聚合物材料,彌補環氧樹脂的不足。 In view of this, there is an urgent need to find a polymer material with high mechanical strength, toughness, and high and low temperature resistance to make up for the shortcomings of epoxy resin.

本發明的目的是提供一種可雙固化的端環氧基聚矽氧烷及其製備方法。 The object of the present invention is to provide a dual-curable terminal epoxy polysiloxane and a preparation method thereof.

在本發明的第一方案,提供了一種端環氧基聚矽氧烷,所述端環氧基聚矽氧烷具式(0)結構: Y-X-Y 式(0);其中,X具有至少四組式(III)結構:-{[OSi(R)2-]k-L}- 式(III);其中,每個R各自獨立地為R1、R2、R3,且k為1至100的正整數,每組的k相同或不相同;其中,R1、R2、R3各自獨立地為經取代或未經取代的選自以下群組的基團:直鏈或支鏈C1-25烷基、直鏈或支鏈C1-25烷氧基、C3-25環烷基、C6-22芳基、5至20元雜芳基、C6-25芳氧基、C2-25環醚基;所述的取代是指被選自以下群組的基團取代:鹵素、羥基、C1-8烷基、C2-8烯基、C6-10芳基;L為-(L1)n-;且各個L1各自獨立地選自以下群組:經取代或未經取代的C1-10伸烷基、經取代或未經取代的C2-30的醯基、經取代或未經取代的C2-30酯基;且各個L1之間各基團間任選地被氧和C6-10的伸芳基間隔;n選自以下群組:1、2、3、4、5、6、7、8、9、10;Y選自以下群組:具有環氧丙基之C2-25直鏈或支鏈烷基、C3-25環氧醚基、及C3-25環烷基,所述環烷基之環上的至少二個碳以-O-結構彼此相連。 In the first aspect of the present invention, a terminal epoxy polysiloxane is provided. The terminal epoxy polysiloxane has the structure of formula (0): YXY formula (0); wherein, X has at least four groups Formula (III) structure: -{[OSi(R) 2 -] k -L}- Formula (III); where each R is independently R 1 , R 2 , R 3 , and k is 1 to 100 is a positive integer, k in each group is the same or different; wherein, R 1 , R 2 , and R 3 are each independently a substituted or unsubstituted group selected from the following groups: linear or branched C 1 -25 alkyl, straight or branched chain C 1-25 alkoxy, C 3-25 cycloalkyl, C 6-22 aryl, 5 to 20 membered heteroaryl, C 6-25 aryloxy, C 2-25 cyclic ether group; the substitution refers to substitution with a group selected from the following groups: halogen, hydroxyl, C 1-8 alkyl, C 2-8 alkenyl, C 6-10 aryl; L is -(L 1 ) n -; and each L 1 is independently selected from the following group: substituted or unsubstituted C 1-10 alkylene, substituted or unsubstituted C 2-30 hydroxyl group, a substituted or unsubstituted C 2-30 ester group; and each group between each L 1 is optionally separated by oxygen and a C 6-10 aryl group; n is selected from the following group: 1 , 2, 3, 4, 5, 6, 7, 8, 9, 10; Y is selected from the following groups: C 2-25 linear or branched alkyl with glycidyl group, C 3-25 epoxy Ether group, and C 3-25 cycloalkyl group, at least two carbons on the ring of the cycloalkyl group are connected to each other with an -O- structure.

在另一較佳態樣中,所述的端環氧基聚矽氧烷具有式(I)結構:

Figure 111144429-A0305-02-0004-1
In another preferred aspect, the epoxy-terminated polysiloxane has the structure of formula (I):
Figure 111144429-A0305-02-0004-1

R1、R2、R3、L、Y如本發明第一方案所定義;s為0或1至100的正整數;q、t各自獨立地為1至100的正整數。 R 1 , R 2 , R 3 , L and Y are as defined in the first aspect of the present invention; s is 0 or a positive integer from 1 to 100; q and t are each independently a positive integer from 1 to 100.

在另一較佳態樣中,R1、R2、R3各自獨立地為經取代或未經取代的選自以下群組的基團:直鏈或支鏈C1-16烷基、直鏈或支鏈C1-16烷氧基、C6-10芳基、C6-10芳氧基;所述的取代是指被選自以下群組的基團取代:鹵素、羥基、C1-8烷基、C2-8烯基、C6-10芳基;L為-(L1)n-;且各個L1各自獨立地選自以下群組:經取代或未經取代的C1-10伸烷基;且各個L之間各基團間任選地被氧和C6-10的伸芳基間隔;n選自以下群組:1、2、3、4、5、6、7、8、9、10;Y選自以下群組:具有環氧丙基之C2-16直鏈或支鏈烷基、C3-16環氧醚基、及C3-16環烷基,所述環烷基之環上的至少二個碳以-O-結構彼此相連。 In another preferred embodiment, R 1 , R 2 , and R 3 are each independently a substituted or unsubstituted group selected from the following groups: linear or branched C 1-16 alkyl, linear Chain or branched C 1-16 alkoxy, C 6-10 aryl, C 6-10 aryloxy; the substitution refers to substitution with a group selected from the following groups: halogen, hydroxyl, C 1 -8 alkyl, C 2-8 alkenyl, C 6-10 aryl; L is -(L 1 ) n -; and each L 1 is independently selected from the following group: substituted or unsubstituted C 1-10 alkylene groups; and each group between each L is optionally separated by oxygen and an aryl group of C 6-10 ; n is selected from the following group: 1, 2, 3, 4, 5, 6 , 7, 8, 9, 10; Y is selected from the following group: C 2-16 linear or branched alkyl group with glycidyl group, C 3-16 epoxy ether group, and C 3-16 cycloalkyl group group, at least two carbons on the ring of the cycloalkyl group are connected to each other in an -O- structure.

在另一較佳態樣中,R1、R2、R3各自獨立地為經取代或未經取代的選自以下群組的基團:直鏈或支鏈C1-8烷基、直鏈或支鏈C1-8烷氧基、C6-10芳基、C6-10芳氧基;所述的取代是指被選自以下群組的基團取代:鹵素、羥基、C1-8烷基、C2-8烯基、C6-10芳基;L為-(L1)n-;且各個L1各自獨立地選自以下群組:經取代或未經取代的C1-4伸烷基;且各個L之間各基團間任選地被氧和C6-10的伸芳基間隔;n選自以下群組:1、2、3、4、5、6、7、8、9、10;Y選自以下群組:具有環氧丙基之C2-8直鏈或支鏈烷基、C3-8環氧醚基、及C3-8環烷基,所述環烷基之環上的至少二個碳以-O-結構彼此相連。 In another preferred embodiment, R 1 , R 2 , and R 3 are each independently a substituted or unsubstituted group selected from the following groups: linear or branched C 1-8 alkyl, linear Chain or branched C 1-8 alkoxy, C 6-10 aryl, C 6-10 aryloxy; the substitution refers to substitution with a group selected from the following groups: halogen, hydroxyl, C 1 -8 alkyl, C 2-8 alkenyl, C 6-10 aryl; L is -(L 1 ) n -; and each L 1 is independently selected from the following group: substituted or unsubstituted C 1-4 alkylene groups; and each group between each L is optionally separated by oxygen and an aryl group of C 6-10 ; n is selected from the following group: 1, 2, 3, 4, 5, 6 , 7, 8, 9, 10; Y is selected from the following group: C 2-8 linear or branched alkyl group with glycidyl group, C 3-8 epoxy ether group, and C 3-8 cycloalkyl group group, at least two carbons on the ring of the cycloalkyl group are connected to each other in an -O- structure.

在另一較佳態樣中,L為-CH2CH2-。 In another preferred aspect, L is -CH 2 CH 2 -.

在另一較佳態樣中,s為0至50的正整數;q、t各自獨立地為1至50的正整數。 In another preferred embodiment, s is a positive integer from 0 to 50; q and t are each independently a positive integer from 1 to 50.

在另一較佳態樣中,s為0至10的正整數;q、t各自獨立地為1至10的正整數。 In another preferred embodiment, s is a positive integer from 0 to 10; q and t are each independently a positive integer from 1 to 10.

在另一較佳態樣中,s為0至2的正整數;q、t各自獨立地為1至2的正整數。 In another preferred embodiment, s is a positive integer from 0 to 2; q and t are each independently a positive integer from 1 to 2.

在另一較佳態樣中,所述的端環氧基聚矽氧烷具有式(II)結構:

Figure 111144429-A0305-02-0006-3
In another preferred aspect, the epoxy-terminated polysiloxane has the structure of formula (II):
Figure 111144429-A0305-02-0006-3

其中,Y選自

Figure 111144429-A0305-02-0006-4
、2-(3,4-環氧基環己基)、及噁丁環基(oxetane group)。 Among them, Y is selected from
Figure 111144429-A0305-02-0006-4
, 2-(3,4-epoxycyclohexyl), and oxetane group.

在另一較佳態樣中,R1為C6-10芳氧基,較佳為苄氧基。 In another preferred embodiment, R 1 is C 6-10 aryloxy group, preferably benzyloxy group.

在另一較佳態樣中,R2為直鏈或支鏈C1-8烷氧基。 In another preferred embodiment, R 2 is a linear or branched C 1-8 alkoxy group.

在另一較佳態樣中,R3為直鏈或支鏈C1-8烷基。 In another preferred embodiment, R 3 is a linear or branched C 1-8 alkyl group.

在另一較佳態樣中,Y為

Figure 111144429-A0305-02-0006-5
(對應於C3-25環氧醚基),或
Figure 111144429-A0305-02-0006-7
(對應於C3-25環烷基,所述的環烷基之環上的至少二個碳以-O-結構彼此相連)。 In another preferred aspect, Y is
Figure 111144429-A0305-02-0006-5
(corresponding to C 3-25 epoxy ether group), or
Figure 111144429-A0305-02-0006-7
(Corresponding to C 3-25 cycloalkyl, at least two carbons on the ring of the cycloalkyl are connected to each other with an -O- structure).

在另一較佳態樣中,所述的端環氧基聚矽氧烷由選自以下群組的單體聚合而成:(a)至少2a組矽氫(聚)矽氧烷分子;

Figure 111144429-A0305-02-0006-8
In another preferred aspect, the epoxy-terminated polysiloxane is polymerized by monomers selected from the following groups: (a) at least 2a groups of silicon hydrogen (poly)siloxane molecules;
Figure 111144429-A0305-02-0006-8

(b)至少2a組端烯基環氧分子Y-CH=CH2;以及(c)至少a組雙烯基(聚)矽氧烷分子;

Figure 111144429-A0305-02-0007-9
(b) at least 2a groups of terminal alkenyl epoxy molecules Y-CH=CH 2 ; and (c) at least a group of dienyl (poly)siloxane molecules;
Figure 111144429-A0305-02-0007-9

其中,R1、R2、R3、Y、s、q和t的定義如本發明第一方案所述;a為1至100的正整數。 Wherein, R 1 , R 2 , R 3 , Y, s, q and t are defined as described in the first aspect of the present invention; a is a positive integer from 1 to 100.

在另一較佳態樣中,(a)所述的矽氫(聚)矽氧烷分子具有聚合單元:

Figure 111144429-A0305-02-0007-10
In another preferred aspect, the silicon hydrogen (poly)siloxane molecule described in (a) has polymerized units:
Figure 111144429-A0305-02-0007-10

(b)所述的雙烯基(聚)矽氧烷分子具有聚合單元:

Figure 111144429-A0305-02-0007-12
(b) The dialkenyl (poly)siloxane molecule has polymerized units:
Figure 111144429-A0305-02-0007-12

(c)所述的端烯基環氧分子Y選自以下群組:具有環氧丙基之C2-25直鏈或支鏈烷基、C3-25環氧醚基、C3-25環烷基,所述的環烷基之環上的至少二個碳以-O-結構彼此相連。 (c) The terminal alkenyl epoxy molecule Y is selected from the following groups: C 2-25 linear or branched alkyl group with glycidyl group, C 3-25 epoxy ether group, C 3-25 Cycloalkyl, at least two carbons on the ring of the cycloalkyl are connected to each other in an -O- structure.

在另一較佳態樣中,所述的端環氧基聚矽氧烷為:

Figure 111144429-A0305-02-0008-13
In another preferred aspect, the terminal epoxy polysiloxane is:
Figure 111144429-A0305-02-0008-13

在本發明的第二方案,提供了一種本發明第一方案所述的端環氧基聚矽氧烷的製備方法,包含以下步驟:(a)在惰性溶劑中,在催化劑的存在下,將等比例的矽氫(聚)矽氧烷分子與端烯基環氧分子Y藉由矽氫加成反應,生成端矽氫結構與環氧基的(聚)矽氧烷分子P,所述端矽氫結構與環氧基的(聚)矽氧烷分子P具有如下式所示的結構;

Figure 111144429-A0305-02-0008-14
In the second aspect of the present invention, there is provided a method for preparing the epoxy-terminated polysiloxane according to the first aspect of the present invention, comprising the following steps: (a) in an inert solvent, in the presence of a catalyst, Equal proportions of silicon hydrogen (poly)siloxane molecules and alkenyl-terminated epoxy molecules Y react through silicon hydrogen addition to generate (poly)siloxane molecules P with terminal silicon hydrogen structures and epoxy groups. The (poly)siloxane molecule P of silicon hydrogen structure and epoxy group has the structure shown in the following formula;
Figure 111144429-A0305-02-0008-14

(b)在惰性溶劑中,在65℃氮氣氛圍下,將等比例的所述的(聚)矽氧烷分子P與雙烯基(聚)矽氧烷分子藉由矽氫加成反應,生成端環氧基聚矽氧烷。所述雙烯基(聚)矽氧烷分子具有如下式所示的結構:

Figure 111144429-A0305-02-0008-15
(b) In an inert solvent, under a nitrogen atmosphere of 65°C, equal proportions of the (poly)siloxane molecule P and the bis-alkenyl (poly)siloxane molecule are reacted by silicon hydrogen addition to form Epoxy-terminated polysiloxane. The bis-alkenyl (poly)siloxane molecule has the structure shown in the following formula:
Figure 111144429-A0305-02-0008-15

在另一較佳態樣中,所述的惰性溶劑選自C2-8醚類溶劑。 In another preferred aspect, the inert solvent is selected from C 2-8 ether solvents.

在另一較佳態樣中,所述的惰性溶劑為四氫呋喃。 In another preferred aspect, the inert solvent is tetrahydrofuran.

在另一較佳態樣中,所述的催化劑為氯化三(三苯基膦)合銠(I)。 In another preferred aspect, the catalyst is tris(triphenylphosphine)rhodium(I) chloride.

在本發明的第三方案,提供了一種組合物A,包含:(i)本發明第一方案所述的端環氧基聚矽氧烷;以及(ii)至少一種陽離子固化樹脂。 In the third aspect of the present invention, there is provided a composition A, comprising: (i) the terminal epoxy polysiloxane according to the first aspect of the present invention; and (ii) at least one cationic curing resin.

在另一較佳態樣中,所述的組合物A中,所述的端環氧基聚矽氧烷的含量為組合物A總重量的0.1至50重量%,較佳為0.1至30重量%,更佳為1至10重量%。 In another preferred aspect, in the composition A, the content of the terminal epoxy polysiloxane is 0.1 to 50% by weight of the total weight of the composition A, preferably 0.1 to 30% by weight. %, more preferably 1 to 10% by weight.

在本發明的第四方案,提供了一種組合物B,包含:(a)至少一種環氧樹脂或丙烯酸樹脂;(b)至少一種陽離子固化樹脂或UV光自由基固化劑;以及(c)本發明第一方案所述的端環氧基聚矽氧烷。 In a fourth aspect of the present invention, a composition B is provided, comprising: (a) at least one epoxy resin or acrylic resin; (b) at least one cationic curing resin or UV light radical curing agent; and (c) this The epoxy-terminated polysiloxane according to the first aspect of the invention.

在另一較佳態樣中,所述的環氧樹脂係選自以下群組:醇類縮水甘油醚環氧樹脂、縮水甘油環氧樹脂、縮水甘油胺環氧樹脂、三聚氰胺環氧樹脂、脂環族環氧樹脂、及其組合。 In another preferred aspect, the epoxy resin is selected from the following group: alcohol glycidyl ether epoxy resin, glycidyl epoxy resin, glycidyl amine epoxy resin, melamine epoxy resin, lipid Cyclic epoxy resins, and combinations thereof.

在另一較佳態樣中,所述的環氧樹脂選自以下群組:環氧樹脂E54、環氧樹脂E44、環氧樹脂E51、及其組合。 In another preferred aspect, the epoxy resin is selected from the following group: epoxy resin E54, epoxy resin E44, epoxy resin E51, and combinations thereof.

所述的丙烯酸樹脂選自以下群組:聚氨酯(甲基)丙烯酸酯(urethane(meth)acrylate)、環氧(甲基)丙烯酸酯(epoxy(meth)acrylate)、醇類丙烯酸酯、聚環氧丙烯酸酯、聚酯丙烯酸酯、丙烯酸酯、及其組合。 The acrylic resin is selected from the following group: urethane (meth) acrylate, epoxy (meth) acrylate, alcohol acrylate, polyepoxy Acrylates, polyester acrylates, acrylates, and combinations thereof.

在另一較佳態樣中,所述的聚氨酯(甲基)丙烯酸酯(urethane(meth)acrylate)選自以下群組:脂肪族聚氨酯(甲基)丙烯酸酯(aliphatic urethane(meth)acrylate)、芳香族聚氨酯(甲基)丙烯酸酯(aromatic urethane(meth)acrylate)、脂肪族聚氨酯二(甲基)丙烯酸酯(aliphatic urethane di(meth)acrylate)、芳香族聚氨酯二(甲基)丙烯酸酯(aromatic urethane di(meth)acrylate)、矽氧烷聚氨酯(甲基)丙烯酸酯(siliconized urethane(meth)acrylate)、脂肪族聚氨酯六(甲基)丙烯酸酯(aliphatic urethane hexa(meth)acrylate)、芳香族聚氨酯六(甲基)丙烯酸酯(aromatic urethane hexa(meth)acrylate)、脂肪族聚氨酯八丙烯酸酯(aliphatic urethane octaacrylate)、芳香族聚氨酯八丙烯酸酯(aromatic urethane octaacrylate)、脂肪族聚氨酯九丙烯酸酯(aliphatic urethane nonaacrylate)、芳香族聚氨酯九丙烯酸酯(aromatic urethane nonaacrylate)、脂肪族聚氨酯十五丙烯酸酯(aliphatic urethane pentadecacrylate)、芳香族聚氨酯十五丙烯酸酯(aromatic urethane pentadecacrylate)、及其組合。 In another preferred aspect, the urethane(meth)acrylate is selected from the following group: aliphatic urethane(meth)acrylate, Aromatic urethane(meth)acrylate, aliphatic urethane di(meth)acrylate, aromatic urethane di(meth)acrylate urethane di(meth)acrylate), siliconized urethane(meth)acrylate, aliphatic urethane hexa(meth)acrylate, aromatic polyurethane aromatic urethane hexa(meth)acrylate, aliphatic urethane octaacrylate, aromatic urethane octaacrylate, aliphatic urethane octaacrylate nonaacrylate), aromatic urethane nonaacrylate, aliphatic urethane pentadecacrylate, aromatic urethane pentadecacrylate, and combinations thereof.

在另一較佳態樣中,所述的環氧(甲基)丙烯酸酯(epoxy(meth)acrylate)選自以下群組:雙酚A環氧二(甲基)丙烯酸酯(bisphenol-A epoxy di(meth)acrylate)、酚醛環氧(甲基)丙烯酸酯(novolac epoxy(meth)acrylate)、及其組合。 In another preferred aspect, the epoxy (meth) acrylate is selected from the following group: bisphenol-A epoxy di(meth)acrylate), novolac epoxy(meth)acrylate, and combinations thereof.

在另一較佳態樣中,所述的聚酯(甲基)丙烯酸酯(polyester(meth)acrylate)選自以下群組:聚酯二(甲基)丙烯酸酯(polyester di(meth) acrylate)、(甲基)丙烯酸酯寡聚物((meth)acrylate oligomer)、及其組合。 In another preferred aspect, the polyester(meth)acrylate is selected from the following group: polyester di(meth)acrylate acrylate), (meth)acrylate oligomer ((meth)acrylate oligomer), and combinations thereof.

在另一較佳態樣中,所述的醇類丙烯酸酯選自以下群組:二季戊四醇五丙烯酸酯(dipentaerythritol pentacrylate)、二季戊四醇六丙烯酸酯(dipentaerythritol hexaacrylate)、山梨糖醇六丙烯酸酯(Sorbitol hexaacrylate)、己內酯改質季戊四醇六丙烯酸酯(caprolactone modified dipentaerythritol hexaacrylate)、3-羥-2,2-二甲基丙酸3-羥-2,2-二甲基丙酯二丙烯酸酯(hydroxypivalyl hydroxypivalate diacrylate)、乙氧化1,6-己二醇二丙烯酸酯(ethoxylated 1,6-hexanediol diacrylate)、二丙二醇二丙烯酸酯(dipropylene glycol diacrylate)、三環癸烷二甲醇二丙烯酸酯(Tricyclodecane dimethanol diacrylate)、乙氧化二丙二醇二丙烯酸酯(ethoxylated dipropylene glycol diacrylate)、新戊二醇二丙烯酸酯(neopentyl glycol diacrylate)、丙氧化新戊二醇二丙烯酸酯(propoxylated neopentyl glycol diacrylate)、乙氧化雙酚A二甲基丙烯酸酯(ethoxylated bisphenol-A dimethacrylate)、2-甲基-1,3-丙二醇二丙烯酸酯(2-methyl-1,3-propanediol diacrylate)、乙氧化-2-甲基-1,3-丙二醇二丙烯酸酯(ethoxylated 2-methyl-1,3-propanediol diacrylate)、2-丁基-2-乙基-1,3-丙二醇二丙烯酸酯(2-butyl-2-ethyl-1,3-propanediol diacrylate)、乙二醇二甲基丙烯酸酯(ethylene glycol dimethacrylate;EGDMA)、二乙二醇二甲基丙烯酸酯(diethylene glycol dimethacrylate)、三(2-羥乙基)異氰脲酸三丙烯酸酯(Tris(2-hydroxy ethyl)isocyanurate triacrylate)、季戊四醇三丙烯酸酯(pentaerythritol triacrylate)、乙氧 化三羥甲基丙烷三丙烯酸酯(ethoxylated trimethylolpropane triacrylate)、丙氧化三羥甲基丙烷三丙烯酸酯(propoxylated trimethylolpropane triacrylate)、三羥甲基丙烷三甲基丙烯酸酯(trimethylolpropane trimethacrylate)、季戊四醇四丙烯酸酯(pentaerythritol tetraacrylate)、乙氧化季戊四醇四丙烯酸酯(ethoxylated pentaerythritol tetraacrylate)、雙-三羥甲基丙烷四丙烯酸酯(ditrimethylolpropane tetraacrylate)、丙氧化季戊四醇四丙烯酸酯(propoxylated pentaerythritol tetraacrylate)、二季戊四醇六丙烯酸酯(dipentaerythritol hexaacrylate)、三丙二醇二甲基丙烯酸酯(tripropylene glycol dimethacrylate)、1,4-丁二醇二甲基丙烯酸酯(1,4-butanediol dimethacrylate)、1,6-己二醇二甲基丙烯酸酯(1,6-hexanediol dimethacrylate)、烯丙基化二甲基丙烯酸環己酯(allylated cyclohexyl dimethacrylate)、二甲基丙烯酸異氰脲酸酯(isocyanurate dimethacrylate)、乙氧基化三羥甲基丙烷三甲基丙烯酸酯(ethoxylated trimethylolpropane trimethacrylate)、丙氧基化甘油三甲基丙烯酸酯(propoxylated glycerol trimethacrylate)、三(丙烯氧乙基)異氰脲酸酯(tris(acryloxyethyl)isocyanurate)、三羥甲基丙烷三丙烯酸酯(trimethylolpropane triacrylate)、及其組合。 In another preferred aspect, the alcohol acrylate is selected from the following group: dipentaerythritol pentacrylate, dipentaerythritol hexaacrylate, sorbitol hexaacrylate hexaacrylate), caprolactone modified dipentaerythritol hexaacrylate, 3-hydroxy-2,2-dimethylpropionic acid 3-hydroxy-2,2-dimethylpropyl diacrylate (hydroxypivalyl hydroxypivalate diacrylate), ethoxylated 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, Tricyclodecane dimethanol diacrylate ), ethoxylated dipropylene glycol diacrylate, neopentyl glycol diacrylate, propoxylated neopentyl glycol diacrylate, ethoxylated bisphenol A Dimethacrylate (ethoxylated bisphenol-A dimethacrylate), 2-methyl-1,3-propanediol diacrylate (2-methyl-1,3-propanediol diacrylate), ethoxylated-2-methyl-1,3 -Ethoxylated 2-methyl-1,3-propanediol diacrylate, 2-butyl-2-ethyl-1,3-propanediol diacrylate (2-butyl-2-ethyl-1,3- propanediol diacrylate), ethylene glycol dimethacrylate (EGDMA), diethylene glycol dimethacrylate (diethylene glycol dimethacrylate), tris(2-hydroxyethyl)isocyanurate triacrylate (Tris(2-hydroxy ethyl)isocyanurate triacrylate), pentaerythritol triacrylate, ethoxy Ethoxylated trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate (pentaerythritol tetraacrylate), ethoxylated pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, propoxylated pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate ( dipentaerythritol hexaacrylate), tripropylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate (1,6-hexanediol dimethacrylate), allylated cyclohexyl dimethacrylate, isocyanurate dimethacrylate, ethoxylated trimethylolpropane trisulfate Methacrylate (ethoxylated trimethylolpropane trimethacrylate), propoxylated glycerol trimethacrylate (propoxylated glycerol trimethacrylate), tris(acryloxyethyl)isocyanurate (tris(acryloxyethyl)isocyanurate), trimethylol Propane triacrylate (trimethylolpropane triacrylate), and combinations thereof.

在另一較佳態樣中,所述的聚環氧丙烯酸酯選自以下群組:聚雙酚A環氧六丙烯酸酯(bisphenol-A epoxy hexaacrylate)、聚酚醛環氧六丙烯酸酯(novolac epoxy hexaacrylate)、及其組合。 In another preferred aspect, the polyepoxy acrylate is selected from the following group: bisphenol-A epoxy hexaacrylate, novolac epoxy hexaacrylate), and combinations thereof.

在另一較佳態樣中,所述的聚酯丙烯酸酯選自以下群組:聚酯六丙烯酸酯(polyester hexaacrylate)、脂肪族改質聚酯六丙烯酸酯(fatty acid modified polyester hexaacrylate)、以聚酯多元醇為基礎之丙烯酸酯(polyester polyol based acrylate)、三聚氰胺六丙烯酸酯(melamine hexaacrylate)、及其組合。 In another preferred aspect, the polyester acrylate is selected from the following group: polyester hexaacrylate, fatty acid modified polyester hexaacrylate, and Polyester polyol based acrylate, melamine hexaacrylate, and combinations thereof.

在另一較佳態樣中,所述的丙烯酸酯選自以下群組:丙烯酸甲酯(methyl acrylate)、甲基丙烯酸甲酯(methyl methacrylate;MMA)、丙烯酸乙酯、甲基丙烯酸丁酯、2-苯氧基乙基丙烯酸酯(2-phenoxy ethyl acrylate)、乙氧化2-苯氧基乙基丙烯酸酯(ethoxylated 2-phenoxy ethyl acrylate)、2-(2-乙氧基乙氧基)乙基丙烯酸酯(2-(2-ethoxyethoxy)ethyl acrylate)、環三羥甲基丙烷甲縮醛丙烯酸酯(cyclic trimethylolpropane formal acrylate)、β-羧乙基丙烯酸酯(β-carboxyethyl acrylate)、月桂酸甲基丙烯酸酯(lauryl methacrylate)、異辛基丙烯酸酯(isooctyl acrylate)、硬脂酸甲基丙烯酸酯(stearyl methacrylate)、異癸基丙烯酸酯(isodecyl acrylate)、異冰片基甲基丙烯酸酯(isoborny methacrylate)、芐基丙烯酸酯(benzyl acrylate)、2-羥基乙基甲基丙烯酸酯磷酸酯(2-hydroxyethyl metharcrylate phosphate)、丙烯酸羥乙酯(hydroxyethyl acrylate,HEA)、甲基丙烯酸-2-羥基乙酯(2-hydroxyethyl methacrylate,HEMA)、丙烯醯嗎啉、及其組合。 In another preferred aspect, the acrylate is selected from the following group: methyl acrylate (methyl acrylate), methyl methacrylate (MMA), ethyl acrylate, butyl methacrylate, 2-phenoxy ethyl acrylate, ethoxylated 2-phenoxy ethyl acrylate, 2-(2-ethoxyethyl acrylate) 2-(2-ethoxyethoxy)ethyl acrylate, cyclic trimethylolpropane formal acrylate, β-carboxyethyl acrylate, methyl laurate lauryl methacrylate, isooctyl acrylate, stearyl methacrylate, isodecyl acrylate, isoborny methacrylate ), benzyl acrylate, 2-hydroxyethyl methacrylate phosphate, hydroxyethyl acrylate (HEA), 2-hydroxyethyl methacrylate (2-hydroxyethyl methacrylate, HEMA), acrylomorpholine, and combinations thereof.

在另一較佳態樣中,所述的丙烯酸樹脂選自以下群組:脂肪族聚氨酯丙烯酸酯、二季戊四醇六丙稀酸酯、丙烯醯嗎啉、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、及其組合。 In another preferred aspect, the acrylic resin is selected from the following group: aliphatic polyurethane acrylate, dipentaerythritol hexaacrylate, acrylomorpholine, methyl acrylate, methyl methacrylate, acrylic acid Ethyl acrylate, butyl acrylate, and combinations thereof.

在另一較佳態樣中,所述的陽離子固化樹脂選自以下群組:3,4-環氧環己基甲酸3',4'-環氧環己甲酯、氧雜環丁環、三乙二醇二乙烯基醚、及其組合。 In another preferred aspect, the cationic curing resin is selected from the following group: 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate, oxetane, trisulfide Ethylene glycol divinyl ether, and combinations thereof.

在另一較佳態樣中,所述的氧雜環丁環為市售品TCM201。 In another preferred aspect, the oxetane is commercially available product TCM201.

在另一較佳態樣中,所述的UV光自由基固化劑選自以下群組:二苯基-(4-苯基硫)苯基鋶六氟磷酸鹽、三芳基硫鎓鹽、及其組合。 In another preferred aspect, the UV light radical curing agent is selected from the following group: diphenyl-(4-phenylthio)phenylsonium hexafluorophosphate, triarylsulfonium salt, and its combination.

在另一較佳態樣中,所述的組合物B中,所述的端環氧基聚矽氧烷的含量為組分(a)和組分(b)總重量的0.1至50重量%,較佳為1至30重量%,更佳為5至20重量%。 In another preferred aspect, in the composition B, the content of the terminal epoxy polysiloxane is 0.1 to 50% by weight of the total weight of component (a) and component (b). , preferably 1 to 30% by weight, more preferably 5 to 20% by weight.

在本發明的第五方案,提供了一種本發明第一方案所述的端環氧基聚矽氧烷的用途,所述的端環氧基聚矽氧烷用於製備塗層、黏合劑和密封劑。 In the fifth aspect of the present invention, there is provided a use of the terminal epoxy polysiloxane according to the first aspect of the present invention. The terminal epoxy polysiloxane is used to prepare coatings, adhesives and Sealant.

在本發明的第六方案,提供了一種本發明第三方案所述的組合物A的用途,所述的組合物A用於製備塗層、黏合劑和密封劑。 In the sixth aspect of the present invention, there is provided a use of the composition A according to the third aspect of the present invention, and the composition A is used to prepare coatings, adhesives and sealants.

在本發明的第七方案,提供了一種本發明第四方案所述的組合物B的用途,所述的組合物B用於製備塗層、黏合劑和密封劑。 In the seventh aspect of the present invention, there is provided a use of the composition B according to the fourth aspect of the present invention, and the composition B is used to prepare coatings, adhesives and sealants.

應理解,在本發明範圍內中,本發明的上述各技術特徵和在下文(如實施例)中具體描述的各技術特徵之間都可以互相組合,從而構成新的或較佳的技術方案。限於篇幅,在此不再一一贅述。 It should be understood that within the scope of the present invention, the above-mentioned technical features of the present invention and the technical features specifically described below (such as embodiments) can be combined with each other to form new or better technical solutions. Due to space limitations, I will not go into details here.

圖1:含氫單封端中間產物A的1H NMR圖; 圖2:乙烯基甲氧基矽烷中間產物B的1H NMR圖;圖3:化合物1的1H NMR圖;圖4:化合物1的FT-IR圖;圖5:含氫單封端中間產物C的1H NMR圖;圖6:化合物2的1H NMR圖;以及圖7:左:配方A的SEM圖;右:化合物1/配方A固化後的SEM圖。 Figure 1: 1 H NMR pattern of hydrogen-containing single-capped intermediate A; Figure 2: 1 H NMR pattern of vinylmethoxysilane intermediate B; Figure 3: 1 H NMR pattern of compound 1; Figure 4: Compound FT-IR pattern of 1; Figure 5: 1 H NMR pattern of hydrogen-containing single-capped intermediate product C; Figure 6: 1 H NMR pattern of compound 2; and Figure 7: Left: SEM image of formulation A; right: compound 1/ SEM image of formula A after curing.

本發明人經過廣泛而深入的研究,首次提供了一種可雙固化的端環氧基聚矽氧烷及其製備方法。本發明的端環氧基聚矽氧烷具有多個交聯基團、黏結力強、能廣泛應用於各種領域;本發明的端環氧基聚矽氧烷的製備方法簡單高效。在此基礎上,完成了本發明。 After extensive and in-depth research, the inventor provided for the first time a dual-curable terminal epoxy-terminated polysiloxane and a preparation method thereof. The terminal epoxy polysiloxane of the present invention has multiple cross-linking groups, strong adhesive force, and can be widely used in various fields; the preparation method of the terminal epoxy polysiloxane of the present invention is simple and efficient. On this basis, the present invention was completed.

術語Terminology

如本文所用,除特別說明之外,術語「取代」指基團上的一個或多個氫原子被選自以下群組的取代基取代:C1至C10烷基、C3至C10環烷基、C1至C10烷氧基、鹵素、羥基、羧基(-COOH)、C1至C10醛基、C2至C10醯基、C2至C10酯基、胺基、及苯基。所述的苯基包括未經取代的苯基或具有1至3個取代基的經取代苯基,所述取代基選自:鹵素、C1至C10烷基、氰基、羥基、硝基、C3至C10環烷基、C1至C10烷氧基、及胺基。 As used herein, unless otherwise stated, the term "substituted" means that one or more hydrogen atoms on a group are replaced with a substituent selected from the following group: C 1 to C 10 alkyl, C 3 to C 10 ring Alkyl group, C 1 to C 10 alkoxy group, halogen, hydroxyl group, carboxyl group (-COOH), C 1 to C 10 aldehyde group, C 2 to C 10 hydroxyl group, C 2 to C 10 ester group, amine group, and phenyl. The phenyl group includes unsubstituted phenyl or substituted phenyl with 1 to 3 substituents, and the substituents are selected from: halogen, C 1 to C 10 alkyl, cyano, hydroxyl, nitro , C 3 to C 10 cycloalkyl group, C 1 to C 10 alkoxy group, and amine group.

如本文所用,術語「C1-25烷基」是指具有1至25個碳原子的直鏈或支鏈烷基,較佳地,具有1至10個碳原子的直鏈或支鏈烷基,例如甲基、乙基、丙基、異丙基、丁基、異丁基、二級丁基、三級丁基、或類似基團。 As used herein, the term "C 1-25 alkyl" refers to a straight or branched chain alkyl group having 1 to 25 carbon atoms, preferably a straight chain or branched chain alkyl group having 1 to 10 carbon atoms. , such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, or similar groups.

如本文所用,術語「C2-25烯基」是指具有2至25個碳原子的直鏈或支鏈烯基,較佳地,具有2至10個碳原子的直鏈或支鏈烯基,例如乙烯、丙烯、異丙烯、丁烯、異丁烯、三級丁烯,或類似基團。 As used herein, the term "C 2-25 alkenyl" refers to a straight or branched chain alkenyl group having 2 to 25 carbon atoms, preferably a straight chain or branched chain alkenyl group having 2 to 10 carbon atoms. , such as ethylene, propylene, isopropylene, butylene, isobutylene, tertiary butylene, or similar groups.

如本文所用,術語「芳基」是指在環上不含雜原子的芳香族環基,所述芳基可以稠合於雜芳基、雜環基或環烷基環上,其中與母體結構連接在一起的環為芳基環。如苯基(即C6芳基或六元芳基)、萘基(即C10芳基或[6+6]芳基)等,其中六元芳基還意在包含六元芳基並5至6元環烷基和六元芳基並5至6元雜環基。術語「[5+6]芳基」是指稠合的6、5雙環體系。芳基較佳為C6至C14芳基,更佳為C6至C10芳基。芳基的實例包括苯基、萘基。芳基可以是任選地經取代的或未經取代的。 As used herein, the term "aryl" refers to an aromatic ring group that does not contain heteroatoms in the ring, which aryl group may be fused to a heteroaryl, heterocyclyl, or cycloalkyl ring, with the parent structure The rings joined together are aryl rings. Such as phenyl (ie C 6 aryl or six-membered aryl), naphthyl (ie C 10 aryl or [6+6] aryl), etc., where the six-membered aryl is also intended to include six-membered aryl and 5 to 6-membered cycloalkyl and 6-membered aryl and 5 to 6-membered heterocyclyl. The term "[5+6]aryl" refers to a fused 6,5 bicyclic ring system. The aryl group is preferably a C 6 to C 14 aryl group, more preferably a C 6 to C 10 aryl group. Examples of aryl groups include phenyl, naphthyl. Aryl groups may be optionally substituted or unsubstituted.

術語「雜芳基」指具有1至3個原子為選自N、S和O之群組的雜原子的環狀芳香基,其可以是單環,也可以是稠環形式。本發明中,雜芳基較佳為5至6元雜芳基。雜芳基的實例包括但不限於:吡啶基、噠嗪基、嘧啶基、吡嗪基、三嗪基、吡咯基、吡唑基、咪唑基、(1,2,3)-三唑基以及(1,2,4)-三唑基、四唑基、呋喃基、噻吩基、異噁唑基、噻唑基、噁唑基等。所述雜芳基可以稠合於芳基、雜環基或環烷基環上,其中與母體結構連接在一起的環為雜芳基環。術語「[5+6]雜芳基」是指稠合的6、5雙環體系,如苯並噻吩基、苯並呋喃基、苯並咪唑基、苯並三唑基、苯並噻唑基、苯並噻二唑基、苯並噁唑基等。 The term "heteroaryl" refers to a cyclic aromatic group having 1 to 3 heteroatoms selected from the group of N, S and O, which may be a single ring or a fused ring. In the present invention, the heteroaryl group is preferably a 5- to 6-membered heteroaryl group. Examples of heteroaryl groups include, but are not limited to: pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, pyrrolyl, pyrazolyl, imidazolyl, (1,2,3)-triazolyl, and (1,2,4)-Triazolyl, tetrazolyl, furyl, thienyl, isoxazolyl, thiazolyl, oxazolyl, etc. The heteroaryl group may be fused to an aryl, heterocyclyl or cycloalkyl ring, where the ring attached to the parent structure is the heteroaryl ring. The term "[5+6]heteroaryl" refers to a fused 6,5 bicyclic ring system, such as benzothienyl, benzofuranyl, benzimidazolyl, benzotriazolyl, benzothiazolyl, benzene Thiadiazolyl, benzoxazolyl, etc.

術語「鹵素」指F、Cl、Br和I。 The term "halogen" refers to F, Cl, Br and I.

在本文中,形成「C1-10」,表示該基團可以具有1個至10個碳原子,例如1個、2個、3個、4個、5個、6個、7個、8個、9個、或10個。 As used herein, the formation of "C 1-10 " means that the group may have from 1 to 10 carbon atoms, such as 1, 2, 3, 4, 5, 6, 7, 8 , 9, or 10.

端環氧基聚矽氧烷Terminated epoxy polysiloxane

本發明的端環氧基聚矽氧烷可用作環氧樹脂的增強增韌劑,藉由分子設計製備相容性好、可以形成海島、互穿聚合物網絡(interpenetrating polymer network,IPN)結構的環氧有機矽,能顯著提高強度與韌性,解決環氧樹脂硬脆的缺點。與傳統橡膠粒子增韌劑相比,本發明的端環氧基聚矽氧烷能顯著提升強度和韌性。 The terminal epoxy polysiloxane of the present invention can be used as a reinforcing and toughening agent for epoxy resin. It has good compatibility through molecular design and can form islands and interpenetrating polymer network (IPN) structures. Epoxy silicone can significantly improve strength and toughness and solve the shortcomings of hard and brittle epoxy resin. Compared with traditional rubber particle toughening agents, the terminal epoxy polysiloxane of the present invention can significantly improve the strength and toughness.

本發明的雙固化端環氧基聚矽氧烷含有多個活性官能基團,固化方式多樣,能充分固化,顯著提升附著力,如化合物1在卷鋼防護漆的應用。 The dual-curing terminal epoxy polysiloxane of the present invention contains multiple active functional groups, has various curing methods, can be fully cured, and significantly improves adhesion, such as the application of compound 1 in coil steel protective paint.

特殊結構的雙固化端環氧基聚矽氧烷可作為特種偶聯劑使用,如化合物1可視為KH560的加強版,作為它的替代品。 Specially structured dual-cured end epoxy polysiloxane can be used as a special coupling agent. For example, compound 1 can be regarded as an enhanced version of KH560 and its substitute.

雙固化端環氧基聚矽氧烷在柔性顯示幕的柔性耐刮擦硬塗層保護膜上具有潛在應用前景。 Dual-cured end epoxy polysiloxane has potential application prospects in flexible scratch-resistant hard-coat protective films for flexible display screens.

雙固化端環氧基聚矽氧烷的塗層應用:實現光/熱陽離子、濕氣雙重固化,實現與各種基材的良好黏附,顯著提升附著力(劃格法黏附測試之附著力可達4B至5B,水煮附著力達4B),所述基材包括但不限於:玻璃基材、金屬氧化物基材、金屬基材和聚合物基材;並可得到具有優異表面硬度的透明耐彎折耐刮擦塗層,顯示其在光電子領域的潛在應用。 Coating application of dual-cured end epoxy polysiloxane: realizes dual curing of light/thermal cations and moisture, achieves good adhesion with various substrates, and significantly improves adhesion (the adhesion of the cross-hatch adhesion test can reach 4B to 5B, boiling adhesion reaches 4B), the substrates include but are not limited to: glass substrates, metal oxide substrates, metal substrates and polymer substrates; and transparent resistant materials with excellent surface hardness can be obtained. Bending scratch-resistant coatings, showing potential applications in optoelectronics.

以添加本發明的端環氧基聚矽氧烷藉由光陽離子-濕氣方式進行固化為例。固化後能提升附著力的原因來自於:1)端環氧基聚矽氧烷分子中之端環氧基進行光陽離子固化交聯;以及2)分子中Si-OMe進行脫甲醇後縮合(濕氣),生成Si-O-Si繼續提升附著力達4B或更高。 Take the addition of the terminal epoxy polysiloxane of the present invention for curing by photocation-moisture method as an example. The reason why the adhesion can be improved after curing comes from: 1) the terminal epoxy groups in the terminal epoxy polysiloxane molecules undergo photocationic curing and cross-linking; and 2) the Si-OMe in the molecules undergoes demethanolization and condensation (wet gas), generating Si-O-Si and continuing to improve the adhesion to 4B or higher.

與現有技術相比,本發明的主要優點包括:Compared with the existing technology, the main advantages of the present invention include:

(1)本發明的端環氧基聚矽氧烷綜合有機矽和環氧樹脂的優點,既有環氧樹脂的力學強度,又有有機矽樹脂的韌性、耐高低溫、耐候和憎水性; (1) The terminal epoxy polysiloxane of the present invention combines the advantages of silicone and epoxy resin. It has the mechanical strength of epoxy resin and the toughness, high and low temperature resistance, weather resistance and hydrophobicity of silicone resin;

(2)本發明的製備方法簡單高效,製備的可變固化聚矽氧烷具有多個交聯基團,黏結力強。 (2) The preparation method of the present invention is simple and efficient, and the variable curable polysiloxane prepared has multiple cross-linking groups and strong adhesive force.

(3)本發明的端環氧基聚矽氧烷可藉由光陽離子-濕氣、光陽離子-熱陽離子、濕氣-熱陽離子等多種固化方式進行固化。 (3) The terminal epoxy polysiloxane of the present invention can be cured by various curing methods such as photocation-moisture, photocation-thermal cation, moisture-thermal cation, etc.

(4)本發明的端環氧基聚矽氧烷可單獨使用也可作為添加劑使用。 (4) The epoxy-terminated polysiloxane of the present invention can be used alone or as an additive.

(5)本發明的端環氧基聚矽氧烷能充分固化,能完全體現材料特性,拓展材料的固化厚度和材料用途,能廣泛應用各種材料和領域。 (5) The terminal epoxy polysiloxane of the present invention can be fully cured, can fully reflect the material properties, expand the cured thickness and material uses of the material, and can be widely used in various materials and fields.

下面結合具體實施例,進一步闡述本發明。應理解,這些實施例僅用於說明本發明而不用於限制本發明的範圍。下列實施例中若未注明具體條件的實驗方法,則通常按照常規條件,或按照製造廠商所建議的條件。除非另外說明,否則百分比和份數係按重量計算。 The present invention will be further described below in conjunction with specific embodiments. It should be understood that these examples are only used to illustrate the invention and are not intended to limit the scope of the invention. In the following examples, if no experimental method with specific conditions is specified, conventional conditions or conditions recommended by the manufacturer are usually followed. Unless otherwise stated, percentages and parts are by weight.

實施例1 化合物1 Example 1 Compound 1

Figure 111144429-A0305-02-0018-16
Figure 111144429-A0305-02-0018-16

(1)含氫單封端中間產物A的合成 (1) Synthesis of hydrogen-containing single-capped intermediate product A

將烯丙基縮水甘油醚(114.14公克,1莫耳)溶於60毫升四氫呋喃待用。將0.03公克氯化三(三苯基膦)合銠(I)(催化劑(Catalyst))和1,1,3,3-四甲基二矽氧烷(171.98公克,1.2莫耳)加入安裝了冷凝管和滴液漏斗的多頸圓底燒瓶。在乾燥的氮氣保護下,50℃下緩慢滴入烯丙基縮水甘油醚/四氫呋喃溶液,攪拌反應8小時。反應結束後旋蒸,蒸出四氫呋喃和未反應的1,1,3,3-四甲基二矽氧烷(此步驟可以回收試劑並降低成本),得到紅棕色含氫單封端中間產物,再經過活性碳除色處理得無色透明液體A。 Dissolve allyl glycidyl ether (114.14 grams, 1 mol) in 60 ml of tetrahydrofuran and set aside. 0.03 g of tris(triphenylphosphine)rhodium(I) chloride (Catalyst) and 1,1,3,3-tetramethyldisiloxane (171.98 g, 1.2 mol) were added to the installed Multi-neck round bottom flask with condenser tube and dropping funnel. Under the protection of dry nitrogen, slowly drop the allyl glycidyl ether/tetrahydrofuran solution at 50°C, and stir for 8 hours. After the reaction is completed, spin evaporate to evaporate tetrahydrofuran and unreacted 1,1,3,3-tetramethyldisiloxane (this step can recover reagents and reduce costs) to obtain a reddish-brown hydrogen-containing single-capped intermediate product. Then undergo color removal treatment with activated carbon to obtain colorless and transparent liquid A.

從圖1之氫譜可以看出,4至5ppm處為Si-H峰;3.4至3.8ppm為醚相鄰的H峰;2.6至3.2ppm處為縮水甘油醚基團三元環中的H峰;1.6ppm處為醚間隔一個亞甲基的H峰;以及0.5ppm為矽氫加成由乙烯基轉化的H峰,0至0.3ppm為Si-CH3的H峰。它們的積分符合分子結構式。因此,成功合成出含氫單封端中間產物A。 It can be seen from the hydrogen spectrum in Figure 1 that the Si-H peak is located at 4 to 5 ppm; the H peak adjacent to the ether is located at 3.4 to 3.8 ppm; and the H peak in the three-membered ring of the glycidyl ether group is located at 2.6 to 3.2 ppm. ; 1.6ppm is the H peak of ether separated by a methylene group; and 0.5ppm is the H peak of silicon hydrogenation converted from vinyl, and 0 to 0.3ppm is the H peak of Si-CH 3 . Their integrals fit the molecular structural formula. Therefore, the hydrogen-containing single-capped intermediate A was successfully synthesized.

(2)乙烯基甲氧基矽烷中間產物B的合成 (2) Synthesis of vinylmethoxysilane intermediate product B

乙烯基三甲氧基矽烷(296.48公克,2莫耳)溶於200毫升四氫呋喃,置於安裝了冷凝管和滴液漏斗的多頸圓底燒瓶。二苯基二羥基矽烷(216.31公克,2莫耳)溶於200毫升四氫呋喃,置於滴液漏斗。在乾燥的氮氣保護下,降溫至-20℃並通入氨氣(催化劑(Catalyst))到乙烯基三甲氧基矽烷/四氫呋喃溶液,攪拌情況下緩慢滴入二苯基二羥基矽烷/四氫呋喃溶液,持續反應8小時。反應結束後藉由真空抽除溶解在反應液的氨氣,旋蒸,得到澄清透明液體中間產物B。 Vinyl trimethoxysilane (296.48 g, 2 mol) was dissolved in 200 ml of tetrahydrofuran and placed in a multi-neck round-bottomed flask equipped with a condenser tube and a dropping funnel. Diphenyldihydroxysilane (216.31 g, 2 mol) was dissolved in 200 ml of tetrahydrofuran and placed in a dropping funnel. Under the protection of dry nitrogen, cool the temperature to -20°C and pass ammonia (Catalyst) into the vinyltrimethoxysilane/tetrahydrofuran solution. Slowly drop in the diphenyldihydroxysilane/tetrahydrofuran solution while stirring. The reaction lasts for 8 hours. After the reaction is completed, the ammonia gas dissolved in the reaction solution is removed by vacuum and evaporated to obtain a clear and transparent liquid intermediate product B.

中間產物B的薄層色譜(TLC)顯示只有一個點,說明其為純淨物。從圖2之氫譜數據可以看出,7至8ppm處為苯基H峰;5至6ppm為乙烯基H峰;以及3至4ppm為甲氧基的H峰。 Thin layer chromatography (TLC) of intermediate product B showed only one spot, indicating that it was pure. It can be seen from the hydrogen spectrum data in Figure 2 that the H peak of phenyl groups is at 7 to 8 ppm; the H peak of vinyl groups is at 5 to 6 ppm; and the H peak of methoxy groups is at 3 to 4 ppm.

(3)化合物1的合成 (3) Synthesis of compound 1

在安裝了冷凝管和滴液漏斗的多頸圓底燒瓶中,置入1莫耳中間產物A、0.5莫耳中間產物B、100毫升四氫呋喃和佔反應體系20ppm的卡式催化劑。在乾燥的氮氣保護下,升溫到65℃,持續攪拌4小時。反應結束後旋蒸,再經過活性碳除色處理得無色透明液體,乾燥後得到化合物1。 In a multi-neck round-bottomed flask equipped with a condenser tube and a dropping funnel, place 1 mol of intermediate product A, 0.5 mol of intermediate product B, 100 ml of tetrahydrofuran and 20 ppm of the cassette catalyst in the reaction system. Under the protection of dry nitrogen, raise the temperature to 65°C and continue stirring for 4 hours. After the reaction is completed, it is rotary evaporated, and then undergoes decolorization treatment with activated carbon to obtain a colorless and transparent liquid. After drying, compound 1 is obtained.

從圖3之氫譜數據可以看出,7至8ppm處為苯基H峰;3.4至3.8ppm為醚相鄰的H峰以及甲氧基H峰;2.6至3.2ppm處為縮水甘油醚基團三元環中的H峰;1.6ppm處為醚間隔一個亞甲基的H峰;以及0.5ppm為矽氫加成由乙烯基轉化的H峰,0至0.3ppm為Si-CH3的H峰。 From the hydrogen spectrum data in Figure 3, we can see that 7 to 8 ppm is the phenyl H peak; 3.4 to 3.8 ppm is the H peak adjacent to the ether and the methoxy H peak; 2.6 to 3.2 ppm is the glycidyl ether group The H peak in the three-membered ring; 1.6 ppm is the H peak of ether separated by a methylene group; and 0.5 ppm is the H peak of silicon hydrogenation converted from vinyl, and 0 to 0.3 ppm is the H peak of Si-CH 3 .

從圖4之FT-IR數據可以看出,3100公分-1(cm-1)以上無Si-OH峰,出現2850公分-1的Si-OMe峰、910公分-1環氧特徵峰、1250公分-1的Si-Me峰,以及1000至1200公分-1的Si-O-Si特徵峰和苯環特徵吸收峰(1600公分-1、1450公分-1)。綜上,成功合成出化合物1。 It can be seen from the FT-IR data in Figure 4 that there is no Si-OH peak above 3100 cm -1 (cm -1 ), but there are Si-OMe peaks at 2850 cm -1 , epoxy characteristic peaks at 910 cm -1 , and 1250 cm-1. -1 Si-Me peak, as well as Si-O-Si characteristic peaks from 1000 to 1200 cm -1 and benzene ring characteristic absorption peaks (1600 cm -1 , 1450 cm -1 ). In summary, compound 1 was successfully synthesized.

實施例2 化合物2 Example 2 Compound 2

Figure 111144429-A0305-02-0021-17
Figure 111144429-A0305-02-0021-17

(1)含氫單封端中間產物C的合成 (1) Synthesis of hydrogen-containing single-capped intermediate product C

將1,2-環氧-4-乙烯基環己烷(124.18公克,1莫耳)溶於60毫升四氫呋喃待用。將0.03公克氯化三(三苯基膦)合銠(I)(催化劑(Catalyst))、和1,1,3,3-四甲基二矽氧烷(171.98公克,1.2莫耳)加入安裝了冷凝管和滴液漏斗的多頸圓底燒瓶。在乾燥的氮氣保護下,50℃下緩慢滴入1,2-環氧-4-乙烯基環己烷/四氫呋喃溶液,攪拌反應8小時。反應結束後旋蒸,蒸出四氫呋喃和未反應的1,1,3,3-四甲基二矽氧烷(此步驟可以回收試劑並降低成本),得到紅棕色含氫單封頭中間產物,再經過活性碳除色處理得無色透明液體C。 Dissolve 1,2-epoxy-4-vinylcyclohexane (124.18 g, 1 mol) in 60 ml of tetrahydrofuran and set aside. Add 0.03 grams of tris(triphenylphosphine)rhodium(I) chloride (Catalyst) and 1,1,3,3-tetramethyldisiloxane (171.98 grams, 1.2 moles) into the installation Multi-neck round bottom flask with condenser and dropping funnel. Under the protection of dry nitrogen, slowly drop the 1,2-epoxy-4-vinylcyclohexane/tetrahydrofuran solution at 50°C, and stir for 8 hours. After the reaction is completed, spin evaporate to evaporate tetrahydrofuran and unreacted 1,1,3,3-tetramethyldisiloxane (this step can recover reagents and reduce costs) to obtain a reddish-brown hydrogen-containing single-headed intermediate product. After color removal treatment with activated carbon, a colorless and transparent liquid C is obtained.

從圖5之氫譜數據可以看出,4至5ppm處為Si-H峰;3.1ppm為環氧環己烷六元環中的環氧H峰;1至2ppm為環己烷H峰;以及0.5ppm為矽氫加成由乙烯基轉化的H峰,0至0.3ppm為Si-CH3的H峰。 It can be seen from the hydrogen spectrum data in Figure 5 that 4 to 5 ppm is the Si-H peak; 3.1 ppm is the epoxy H peak in the six-membered ring of epoxycyclohexane; 1 to 2 ppm is the cyclohexane H peak; and 0.5ppm is the H peak converted from vinyl by hydrogenation of silicon, and 0 to 0.3ppm is the H peak of Si-CH 3 .

(2)乙烯基甲氧基矽烷中間產物B的合成如實施例1中所述。 (2) The synthesis of vinylmethoxysilane intermediate B is as described in Example 1.

(3)化合物2的合成 (3) Synthesis of compound 2

在安裝了冷凝管和滴液漏斗的多頸圓底燒瓶中,置入1莫耳中間產物C、0.5莫耳中間產物B、100毫升四氫呋喃和佔反應體系20ppm的卡式催化劑。在乾燥的氮氣保護下,升溫到65℃,持續攪拌反應4小時。反應結束後旋蒸,再經過活性碳除色處理得無色透明液體,乾燥後得到化合物2。 In a multi-necked round-bottomed flask equipped with a condenser tube and a dropping funnel, place 1 mol of intermediate product C, 0.5 mol of intermediate product B, 100 ml of tetrahydrofuran and 20 ppm of the cassette catalyst in the reaction system. Under the protection of dry nitrogen, the temperature was raised to 65°C and the reaction was continued with stirring for 4 hours. After the reaction is completed, it is rotary evaporated, and then undergoes color removal treatment with activated carbon to obtain a colorless and transparent liquid. After drying, compound 2 is obtained.

從圖6氫譜數據可以看出,7至8ppm處為苯基H峰;3至4ppm為環氧環己烷六元環中的環氧H峰以及甲氧基H峰;1至2ppm處為環己烷六元環中的亞甲基H峰;以及0.5ppm為矽氫加成由乙烯基轉化的H峰,0至0.3ppm為Si-CH3的H峰。 It can be seen from the hydrogen spectrum data in Figure 6 that the phenyl H peak is at 7 to 8 ppm; the epoxy H peak and the methoxy H peak in the six-membered ring of epoxycyclohexane are at 3 to 4 ppm; and the phenyl H peak is at 1 to 2 ppm. The H peak of methylene in the six-membered ring of cyclohexane; and 0.5ppm is the H peak converted from vinyl by silicon hydrogenation, and 0 to 0.3ppm is the H peak of Si-CH 3 .

實施例3 增韌性Example 3 Toughness enhancement

本實施例1提供的化合物1在環氧樹脂增強增韌的應用。 This Example 1 provides the application of Compound 1 in reinforcing and toughening epoxy resin.

配置雙酚A類環氧膠配方A,其中主劑:環氧樹脂E54(無錫鳳凰牌)80份、端羧基丁腈橡膠(深圳市瑪斯尼彈性有限公司)15份、γ-環氧丙氧基三甲氧基矽烷(日本信越)0.8份、親水白碳黑AERSOIL380(德國贏創)5份;以及固化劑:聚醯胺固化劑(德國贏創910)35份、聚醯胺固化劑(德國贏創350)35份、800目氫氧化鋁粉末(中國鋁業)30份。 Configure bisphenol A epoxy adhesive formula A, in which the main agent is: 80 parts of epoxy resin E54 (Wuxi Phoenix Brand), 15 parts of carboxyl-terminated nitrile rubber (Shenzhen Masni Elastic Co., Ltd.), γ-epoxy propylene 0.8 parts of oxytrimethoxysilane (Shin-Etsu, Japan), 5 parts of hydrophilic white carbon black AERSOIL380 (Evonik, Germany); and curing agent: 35 parts of polyamide curing agent (Evonik 910, Germany), polyamide curing agent ( 35 parts of German Evonik 350) and 30 parts of 800 mesh aluminum hydroxide powder (China Aluminum).

分別攪勻主劑和固化劑後,靜置待用,以配方A作為對照組。 Mix the main agent and curing agent thoroughly, then let them stand for use. Formula A is used as the control group.

以配方A加化合物1作為實驗組,精確稱量化合物1,加入上述配方A中的主劑,攪拌均勻;再加入上述配方A中的固化劑,攪拌均勻;其中化合物1佔總質量的4.25%。 Use formula A plus compound 1 as the experimental group, accurately weigh compound 1, add the main agent in the above formula A, and stir evenly; then add the curing agent in the above formula A, stir evenly; compound 1 accounts for 4.25% of the total mass. .

實驗手法:選用拉伸模具或剪切模具,分別取10公克等量的配方A和配方A/化合物1,分別塗抹模具表面,撒上鋯珠固定膜厚,模具貼合後用夾子固定,置於烘箱40℃24小時固化後,在25℃下測定。 Experimental technique: Use a stretching mold or shearing mold, take 10 grams of equal amounts of Formula A and Formula A/Compound 1 respectively, apply them on the surface of the mold respectively, sprinkle zirconium beads to fix the film thickness, fix the mold with a clip after fitting, and place After curing in an oven at 40°C for 24 hours, measure at 25°C.

Figure 111144429-A0305-02-0023-18
Figure 111144429-A0305-02-0023-18

Figure 111144429-A0305-02-0023-19
Figure 111144429-A0305-02-0023-19

結果顯示,添加少量化合物1到配方A,固化後抗拉強度提升116%,剪切強度提升36%,同時伸長率、拉伸和剪切模量也有所提高。化合物1在其中發揮增強增韌添加劑的作用。 The results showed that adding a small amount of Compound 1 to Formula A increased the tensile strength by 116% and the shear strength by 36% after curing. At the same time, the elongation, tensile and shear modulus also increased. Compound 1 plays the role of reinforcing and toughening additive.

圖7之電子顯微鏡掃描圖可看出,配方A幾乎無海島結構,引入化合物1後形成大小均勻的海島結構,顯著提高了力學性能。 It can be seen from the electron microscope scanning image in Figure 7 that formula A has almost no island structure. After the introduction of compound 1, an island structure of uniform size is formed, which significantly improves the mechanical properties.

實施例4Example 4

本實施例1提供化合物1作為UV陽離子固化樹脂的應用實例。 This Example 1 provides an application example of compound 1 as a UV cationic curable resin.

將化合物1引入UV陽離子固化評測基本配方,檢驗其在不同基材的附著力。3,4-環氧環己基甲酸3',4'-環氧環己甲酯在紫外光固化體系具有固化速度快、節能、生產效率高、固化後機械性能好等優點,在塗料、封裝材料等得到廣泛應用。因此引入3,4-環氧環己基甲酸3',4'-環氧環己甲酯作為比較例。 Compound 1 was introduced into the basic formula for UV cationic curing evaluation to test its adhesion on different substrates. 3,4-Epoxycyclohexylcarboxylic acid 3',4'-epoxycyclohexylmethyl ester has the advantages of fast curing speed, energy saving, high production efficiency, and good mechanical properties after curing in the UV curing system. It is widely used in coatings and packaging materials. etc. are widely used. Therefore, 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexylcarboxylate is introduced as a comparative example.

根據文獻「3,4-環氧環己基甲酸3',4'-環氧環己甲酯的製備」(馮韶靜、宋玉婉、熊健西、肖亞平,合成樹脂及塑膠,2018,35(6):10)在實驗室合成3,4-環氧環己基甲酸3',4'-環氧環己甲酯,產物純化前後純度為95%和97%,分別標為C(未純化)和D(純化)。 According to the literature "Preparation of 3',4'-epoxycyclohexyl methyl ester of 3,4-epoxycyclohexylcarboxylate" (Feng Shaojing, Song Yuwan, Xiong Jianxi, Xiao Yaping, Synthetic Resins and Plastics, 2018, 35(6): 10) 3,4-Epoxycyclohexylcarboxylic acid 3',4'-epoxycyclohexylmethyl ester was synthesized in the laboratory. The purity of the products before and after purification were 95% and 97%, respectively labeled C (unpurified) and D (purified). .

UV陽離子固化評測基本配方組成為:化合物1或C、D佔70份,TCM201(氧雜環丁烷)佔30份,PAG201(三芳基硫鎓鹽)佔5份,增感劑PSS701佔0.5份。TCM201、PAG201、PSS701均採購自常州強力電子新材料股份有限公司。UV固化後用百格法評測附著力,以0B至5B為標準,數據越大說明附著力越好。其結果如表3所示。 The basic formula for UV cationic curing evaluation is as follows: Compound 1 or C and D account for 70 parts, TCM201 (oxetane) accounts for 30 parts, PAG201 (triarylsulfonium salt) accounts for 5 parts, and sensitizer PSS701 accounts for 0.5 parts . TCM201, PAG201, and PSS701 were all purchased from Changzhou Qianli Electronic New Materials Co., Ltd. After UV curing, use the hundred grid method to evaluate the adhesion, using 0B to 5B as the standard. The larger the data, the better the adhesion. The results are shown in Table 3.

Figure 111144429-A0305-02-0024-20
Figure 111144429-A0305-02-0024-20

UV陽離子基本配方評測結果顯示,化合物1作為UV陽離子固化樹脂具有UV固化時間短,在多種基材都有優異的附著力,特別在是配方附著差的基材,如打磨馬口鐵、玻璃、PMMA和PET,具有廣闊的使用範圍。 The evaluation results of the basic UV cationic formula show that Compound 1, as a UV cationic curing resin, has short UV curing time and excellent adhesion on a variety of substrates, especially substrates with poor adhesion of the formula, such as polished tinplate, glass, PMMA and PET has a wide range of uses.

UV卷鋼自由基防護漆體系中,由於固化時收縮嚴重,對金屬基材難附著。自由基體系中引入低收縮的陽離子固化體系(如:化合物1)有利改善其漆膜性能,提升附著力。 In the UV coil steel free radical protective paint system, due to severe shrinkage during curing, it is difficult to adhere to the metal substrate. The introduction of low-shrinkage cationic curing system (such as compound 1) into the free radical system will help improve the paint film properties and enhance adhesion.

在鍍鋅卷鋼基材上輥塗含10重量%化合物1的UV陽離子固化評測基本配方的自由基底漆(約15至20微米),然後UV曝光,再輥塗面漆(約15至20微米),最後UV曝光固化。 A free radical primer (approximately 15 to 20 microns) containing 10% by weight of Compound 1 of the basic formula for UV cationic curing evaluation was rolled on the galvanized coiled steel substrate, followed by UV exposure, and then the topcoat (approximately 15 to 20 μm) was rolled micron), and finally UV exposure and curing.

其中底漆配方為:脂肪族聚氨酯丙烯酸酯60份(DR-U315,長興材料工業有限公司),二季戊四醇六丙稀酸酯11份(EM265,長興材料工業有限公司),丙烯醯嗎啉17份(ACMO,江西洛特化工有限公司),光引發劑184為3份(上海凱茵化工有限公司),TiO2為9份(常州全通化工),化合物1之UV陽離子固化評測基本配方10份。其中,所述的化合物1的UV陽離子固化評測基本配方組成為:化合物1佔70份,TCM201佔30份,PAG201佔5份,增感劑PSS701佔0.5份。 The primer formula is: 60 parts of aliphatic polyurethane acrylate (DR-U315, Changxing Materials Industry Co., Ltd.), 11 parts of dipentaerythritol hexaacrylate (EM265, Changxing Materials Industry Co., Ltd.), and 17 parts of acrylomorpholine (ACMO, Jiangxi Luote Chemical Co., Ltd.), photoinitiator 184 is 3 parts (Shanghai Kaiyin Chemical Co., Ltd.), TiO 2 is 9 parts (Changzhou Quantong Chemical), and the basic formula of UV cationic curing evaluation of compound 1 is 10 parts . Among them, the basic formula for the UV cationic curing evaluation of compound 1 is as follows: compound 1 accounts for 70 parts, TCM201 accounts for 30 parts, PAG201 accounts for 5 parts, and sensitizer PSS701 accounts for 0.5 parts.

面漆配方為:脂肪族聚氨酯丙烯酸酯60份(DR-U315,長興材料工業有限公司),丙烯醯嗎啉15份(ACMO,江西洛特化工有限公司),光引發劑TPO為5份(濟南威振化工),光引發劑819為1份(上海凱茵化工有限公司),畢克流平劑1份(BYK333,深圳市大洋新材料有限公司),TiO2為30份(常州全通化工)。 The topcoat formula is: 60 parts of aliphatic polyurethane acrylate (DR-U315, Changxing Materials Industry Co., Ltd.), 15 parts of acrylomorpholine (ACMO, Jiangxi Lote Chemical Co., Ltd.), and 5 parts of photoinitiator TPO (Jinan Weizhen Chemical), 1 part of photoinitiator 819 (Shanghai Kaiyin Chemical Co., Ltd.), 1 part of BYK leveling agent (BYK333, Shenzhen Dayang New Materials Co., Ltd.), 30 parts of TiO 2 (Changzhou Quantong Chemical Co., Ltd. ).

固化後測試膜厚,並對其衝擊、彎折性能進行評估並整理於表4。採用百格法測試附著力,以0B至5B為標準。數據越大說明附著力越好。評估固化後的附著力以及固化後繼續測試100℃/1小時的附著力。 After curing, the film thickness was tested, and its impact and bending properties were evaluated and summarized in Table 4. Use the hundred grid method to test the adhesion, with 0B to 5B as the standard. The larger the data, the better the adhesion. Evaluate the adhesion after curing and continue to test the adhesion at 100°C/1 hour after curing.

Figure 111144429-A0305-02-0026-21
Figure 111144429-A0305-02-0026-21

將含化合物1的UV陽離子配方引入底漆對水煮有明顯的改善作用。數據越大說明附著力越好。底漆配方UV固化後耐水煮為0B,引入含化合物1的UV陽離子配方固化後上升到4B,說明顯著改善了底漆耐水煮的附著力。將固化後的樣品繼續室溫放置7天,或者60℃烘1小時,百格法測試發現附著力能由原4B提升到5B。後固化能提升附著力的原因來自於端環氧基聚矽氧烷分子中Si-OMe脫甲醇後繼續縮合,生成Si-O-Si。 Introducing a UV cationic formulation containing Compound 1 into the primer had a significant improvement in boiling. The larger the data, the better the adhesion. The water boiling resistance of the primer formula after UV curing was 0B, and the UV cationic formula containing compound 1 was introduced and rose to 4B after curing, indicating that the adhesion of the primer against water boiling was significantly improved. The cured sample was left at room temperature for 7 days, or baked at 60°C for 1 hour. The 100-meter test found that the adhesion could be improved from the original 4B to 5B. The reason why post-curing can improve adhesion comes from the Si-OMe in the terminal epoxy polysiloxane molecules being demethanolized and then condensing to form Si-O-Si.

在本發明提及的所有文獻都在本申請中引用作為參考,就如同每一篇文獻被單獨引用作為參考。此外應理解,在閱讀了本發明的上述講授內容之後,本領域技術人員可以對本發明作各種改動或修改,這些等價形式同樣落於本申請所附申請專利範圍所界定的範圍。 All documents mentioned in this application are incorporated by reference in this application to the same extent as if each individual document was individually incorporated by reference. In addition, it should be understood that after reading the above teaching 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 fall within the scope defined by the patent scope attached to this application.

Claims (9)

一種端環氧基聚矽氧烷,其中,該端環氧基聚矽氧烷具有式(0)結構:Y-X-Y 式(0);其中,X具有至少四組式(III)結構:-{[OSi(R)2-]k-L}- 式(III);其中,每個R各自獨立地為R1、R2、R3,且k為1至100的正整數,每組的k相同或不相同;其中,R1、R2、R3各自獨立地為經取代或未經取代的選自以下群組的基團:直鏈或支鏈C1-25烷基、直鏈或支鏈C1-25烷氧基、C3-25環烷基、C6-22芳基、5至20元雜芳基、C6-25芳氧基、及C2-25環醚基;該取代是指被選自以下群組的基團取代:鹵素、羥基、C1-8烷基、C2-8烯基、及C6-10芳基;L為-(L1)n-;且各個L1各自獨立地選自以下群組:經取代或未經取代的C1-10伸烷基、經取代或未經取代的C2-30的醯基、及經取代或未經取代C2-30的酯基;且各個L1之間各基團間任選地被氧和C6-10的伸芳基間隔;n選自以下群組:1、2、3、4、5、6、7、8、9、及10;Y選自以下群組:具有環氧丙基之C2-25直鏈或支鏈烷基、C3-25環氧醚基、及C3-25環烷基,其中,該環烷基之環上的至少二個碳以-O-結構彼此相連。 A kind of terminal epoxy polysiloxane, wherein, the terminal epoxy polysiloxane has formula (0) structure: YXY formula (0); wherein, X has at least four groups of formula (III) structures: -{[ OSi(R) 2 -] k -L}- Formula (III); where each R is independently R 1 , R 2 , R 3 , and k is a positive integer from 1 to 100, and k in each group is the same Or different; wherein, R 1 , R 2 , R 3 are each independently a substituted or unsubstituted group selected from the following groups: linear or branched C 1-25 alkyl, linear or branched Chain C 1-25 alkoxy group, C 3-25 cycloalkyl group, C 6-22 aryl group, 5 to 20 membered heteroaryl group, C 6-25 aryloxy group, and C 2-25 cyclic ether group; the Substitution means substitution with a group selected from the following group: halogen, hydroxyl, C 1-8 alkyl, C 2-8 alkenyl, and C 6-10 aryl; L is -(L 1 ) n -; And each L 1 is independently selected from the following group: substituted or unsubstituted C 1-10 alkylene group, substituted or unsubstituted C 2-30 acyl group, and substituted or unsubstituted C 2-30 ester group; and each group between each L 1 is optionally separated by oxygen and C 6-10 aryl group; n is selected from the following group: 1, 2, 3, 4, 5 , 6, 7, 8, 9, and 10; Y is selected from the following group: C 2-25 linear or branched alkyl group with glycidyl group, C 3-25 epoxy ether group, and C 3- 25 cycloalkyl, wherein at least two carbons on the ring of the cycloalkyl are connected to each other in an -O- structure. 如請求項1所述的端環氧基聚矽氧烷,其中,該端環氧基聚矽氧烷具有式(I)結構:
Figure 111144429-A0305-02-0028-22
R1、R2、R3、L、Y如請求項1所定義;s為0或1至100的正整數;以及q、t各自獨立地為1至100的正整數。
The terminal epoxy polysiloxane as described in claim 1, wherein the terminal epoxy polysiloxane has the structure of formula (I):
Figure 111144429-A0305-02-0028-22
R 1 , R 2 , R 3 , L and Y are as defined in claim 1; s is 0 or a positive integer from 1 to 100; and q and t are each independently a positive integer from 1 to 100.
如請求項1所述的端環氧基聚矽氧烷,其中,該端環氧基聚矽氧烷具有式(II)結構:
Figure 111144429-A0305-02-0028-23
其中,Y選自
Figure 111144429-A0305-02-0028-24
、2-(3,4-環氧基環己基)、及噁丁環基。
The epoxy-terminated polysiloxane as described in claim 1, wherein the epoxy-terminated polysiloxane has the structure of formula (II):
Figure 111144429-A0305-02-0028-23
Among them, Y is selected from
Figure 111144429-A0305-02-0028-24
, 2-(3,4-epoxycyclohexyl), and oxbutanyl.
如請求項1所述的端環氧基聚矽氧烷,其中,該端環氧基聚矽氧烷由選自以下群組的單體聚合而成:(a)至少2a組矽氫(聚)矽氧烷分子;
Figure 111144429-A0305-02-0028-27
(b)至少2a組端烯基環氧分子Y-CH=CH2;以及(c)至少a組雙烯基(聚)矽氧烷分子;
Figure 111144429-A0305-02-0028-28
其中, R1、R2、R3、Y、s、q和t的定義如請求項1中所述;以及a為1至100的正整數。
The epoxy-terminated polysiloxane as described in claim 1, wherein the epoxy-terminated polysiloxane is polymerized from monomers selected from the following groups: (a) at least 2a groups of silicon hydrogen (polysiloxane) ) siloxane molecule;
Figure 111144429-A0305-02-0028-27
(b) at least 2a groups of terminal alkenyl epoxy molecules Y-CH=CH 2 ; and (c) at least a group of dienyl (poly)siloxane molecules;
Figure 111144429-A0305-02-0028-28
Wherein, R 1 , R 2 , R 3 , Y, s, q and t are defined as described in claim 1; and a is a positive integer from 1 to 100.
如請求項1所述的端環氧基聚矽氧烷,其中,該端環氧基聚矽氧烷為:
Figure 111144429-A0305-02-0029-29
The epoxy-terminated polysiloxane as described in claim 1, wherein the epoxy-terminated polysiloxane is:
Figure 111144429-A0305-02-0029-29
一種含端環氧基聚矽氧烷之組合物,包含:(i)如請求項1至5中任一項所述的端環氧基聚矽氧烷;以及(ii)至少一種陽離子固化樹脂。 A composition containing terminal epoxy polysiloxane, comprising: (i) the terminal epoxy polysiloxane as described in any one of claims 1 to 5; and (ii) at least one cationic curing resin . 一種含端環氧基聚矽氧烷之組合物,包含:(a)至少一種環氧樹脂或丙烯酸樹脂;(b)至少一種陽離子固化樹脂或UV光自由基固化劑;以及(c)請求項1至5中任一項所述的端環氧基聚矽氧烷。 A composition containing terminal epoxy group polysiloxane, comprising: (a) at least one epoxy resin or acrylic resin; (b) at least one cationic curing resin or UV light radical curing agent; and (c) claim The epoxy-terminated polysiloxane according to any one of 1 to 5. 如請求項7所述的組合物,其中該端環氧基聚矽氧烷的含量為組分(a)和組分(b)總重量的0.1至50重量%。 The composition of claim 7, wherein the content of the terminal epoxy polysiloxane is 0.1 to 50% by weight based on the total weight of component (a) and component (b). 一種如請求項1所述的端環氧基聚矽氧烷的用途,其係用於製備塗層、黏合劑和密封劑。 A use of the terminal epoxy polysiloxane as described in claim 1, which is used to prepare coatings, adhesives and sealants.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111234234A (en) * 2018-11-28 2020-06-05 万华化学集团股份有限公司 UV/moisture dual-curing polysiloxane and preparation method and application thereof
CN113929874A (en) * 2021-11-16 2022-01-14 华东理工大学华昌聚合物有限公司 Epoxy resin composition and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111234234A (en) * 2018-11-28 2020-06-05 万华化学集团股份有限公司 UV/moisture dual-curing polysiloxane and preparation method and application thereof
CN113929874A (en) * 2021-11-16 2022-01-14 华东理工大学华昌聚合物有限公司 Epoxy resin composition and preparation method thereof

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