TW202406994A - 聚矽氧烷填料處理劑及由其製備之組成物 - Google Patents
聚矽氧烷填料處理劑及由其製備之組成物 Download PDFInfo
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- 239000000945 filler Substances 0.000 title claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 16
- -1 Polysiloxane Polymers 0.000 title claims description 24
- 239000000203 mixture Substances 0.000 title abstract description 33
- 229920001296 polysiloxane Polymers 0.000 title description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims description 2
- 238000010168 coupling process Methods 0.000 claims description 2
- 238000005859 coupling reaction Methods 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 238000009472 formulation Methods 0.000 abstract description 22
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 229940065472 octyl acrylate Drugs 0.000 description 17
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 17
- 239000002245 particle Substances 0.000 description 17
- 238000001125 extrusion Methods 0.000 description 15
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 239000012530 fluid Substances 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000007429 general method Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 125000006850 spacer group Chemical group 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- 238000009966 trimming Methods 0.000 description 2
- KBQVDAIIQCXKPI-UHFFFAOYSA-N 3-trimethoxysilylpropyl prop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C=C KBQVDAIIQCXKPI-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 239000013523 DOWSIL™ Substances 0.000 description 1
- 229920013731 Dowsil Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- RREGISFBPQOLTM-UHFFFAOYSA-N alumane;trihydrate Chemical compound O.O.O.[AlH3] RREGISFBPQOLTM-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- QCAWEPFNJXQPAN-UHFFFAOYSA-N methoxyfenozide Chemical compound COC1=CC=CC(C(=O)NN(C(=O)C=2C=C(C)C=C(C)C=2)C(C)(C)C)=C1C QCAWEPFNJXQPAN-UHFFFAOYSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 230000003534 oscillatory effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000001542 size-exclusion chromatography Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- 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
- C08G77/48—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
-
- 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
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
-
- 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
- C08G77/48—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 in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/54—Nitrogen-containing linkages
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/14—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
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- 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
- C08G77/04—Polysiloxanes
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- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
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- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups
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Abstract
本發明係關於一種式I之填料處理劑：
其中R
1、R
1 '、R
2、R
2 '、m、n、p、及q係如本文所定義。該填料處理劑適用作導熱調配物之添加劑。
Description
本發明係關於一種基於聚矽氧烷之填料處理劑及其在導熱調配物中之應用。
對導熱複合材料之需求的增加推動了導熱調配物的發現，該等導熱調配物為積體電路、電池組、微電子電路、及電動機提供更均勻及更高效的散熱作用。習知導熱調配物之主要組分為基質聚合物、無機填料粒子及填料處理劑(filler treating agent, FTA)。無機粒子為導熱調配物中成本最低的組分，且提供散熱作用。因此，需要將高含量之填料粒子裝載且均勻地分散至基質聚合物中；然而，均勻分散具有挑戰性，因為填料粒子通常與基質聚合物不相容，從而導致相分離。具有與基質聚合物及填料粒子兩者相容之化學官能基的FTA促進相容性，且藉由與無機粒子之表面結合，改良填料粒子之分散性。市售FTA之實例係由以下式表示之單三甲氧基矽氧基封端之聚二甲基矽氧烷：
（參見US 7,592,383 B2，第6欄）；遺憾地，雖然此類FTA以及其他結構類似之FTA具有高效能，但其成本較高，因為其係藉由多步合成程序製備的，需要使用有毒試劑及溶劑，以及大量的純化步驟。因此，在用於導熱調配物之相容劑之本領域中，發現具有可接受效能特性，包括擠壓流量、擠出速率、及黏度之相對較低成本的FTA將為有利的。
本發明藉由提供式I之填料處理劑來解決本領域需求：
I
其中m係5至150；n係0.1至5；p係0至5；q係1至6；X係S或NR
6；各R
1獨立地係C
1-C
6烷基、乙烯基、苯基、或苯甲基；各R
'獨立地係C
1-C
6烷基；
R
2係：
R
2'係：
其中R
3係H或甲基；各R
4獨立地係C
1-C
6烷基；a係1至3之整數；R
5係C
1-C
12烷基；R
6係H或C
1-C
6烷基；且虛線表示連接至X之點。
本發明之FTA適用作導熱調配物之添加劑。
本發明係一種式I之填料處理劑：
I
其中m係5至150；n係0.1至5；p係0至5；q係1至6；X係S或NR
6；各R
1獨立地係C
1-C
6烷基、乙烯基、苯基、或苯甲基；各R
'獨立地係C
1-C
6烷基；
R
2係：
R
2'係：
其中R
3係H或甲基；各R
4獨立地係C
1-C
6烷基；a係1至3之整數；R
5係C
1-C
12烷基；R
6係H或C
1-C
6烷基；且虛線表示連接至X之點。
式I之FTA係隨機共聚物；亦即，具有下標m、n、及p的結構單元不需要呈式I中描繪的順序。較佳地，m係20、或50至較佳125；較佳地，n係0.5、或1、或1.2、或1.5至5、或至3、或至2；p係0、或0.3、或0.5至5、或至3、或至2、或至1；q係1、或2至6、或至4；各R
1較佳獨立地係C
1-C
6烷基，更佳地係甲基或乙基，且最佳地係甲基；R
3較佳地係H；R
4較佳地係甲基或乙基，更佳地係甲基；a較佳地係2或3。適合R
5基團之實例包括甲基、乙基、正丁基、三級丁基、正己基、2-乙基己基、及正辛基。R
6較佳地係H或甲基，更佳地係H。
本發明之填料處理劑可藉由使式IIa化合物：
Ia
與式IIb之丙烯酸酯或甲基丙烯酸酯：
Ib
在偶合催化劑（諸如二甲基苯基膦）存在下接觸而製備式I化合物，其中p係0；且n'係0.1至10。
替代地，式Ia化合物可在相同條件下與式Ib化合物及式Ic化合物：
Ic
接觸以形成式II化合物，其中p＞0。
在另一態樣中，本發明為一種組成物，其包含FTA、聚有機矽氧烷、及填料粒子。聚有機矽氧烷較佳地具有在40至800範圍內的聚合度，且可用例如一或多個可交聯基團，諸如末端乙烯基官能化。此類官能化聚有機矽氧烷之實例包括單乙烯基-二-C
1-C
6烷基封端之聚矽氧烷及雙(乙烯基-二-C
1-C
6烷基)封端之聚矽氧烷，更特定言之，雙(乙烯基-二甲基)封端之聚矽氧烷，其可如US 4,329,273中所述製備。
填料粒子為金屬、金屬氧化物、金屬水合物或陶瓷氮化物粒子，諸如鋁、氧化鋁(aluminum oxide/alumina)、三水合鋁、氮化硼或氧化鋅粒子。如使用HELOS雷射繞射裝置所判定，填料粒子之粒度D
50通常在0.5 µm至100 µm範圍內。第一填料粒子及第二填料粒子之多峰（例如雙峰）分佈可用於調配物中以提高填料粒子濃度。
以組成物之重量計，聚有機矽氧烷之濃度較佳在1.9或5 wt.%至15、或至10 wt.%範圍內；以組成物之重量計，FTA濃度較佳地在0.1、或0.2、或0.3 wt.%至1、或至0.7、或至0.5 wt.%範圍內；且以組成物之重量計，填料裝載量較佳在70、或80、或85、或90 wt.%至98、或至94 wt.%範圍內。已發現由FTA產生的本發明之經調配組成物具有有利的擠壓流動速率、黏度、擠出速率及導熱率。
實例
尺寸排阻層析法
利用液相層析法用Agilent 1260 Infinity II等度泵、多管柱恆溫器、整合式脫氣機、自動取樣器、及折射率偵測器進行SEC分離。系統配備有兩個PLgel Mixed A管柱（300 ×7.5 mm i.d.，粒度=20 µm）及保護管柱(50 ×7.5 mm i.d.)。管柱烘箱及折射率偵測器在40℃下操作。樣本注射體積為100 µL且用THF作為溶離劑以1.0 mL/min之流動速率進行分離。將儀器用580至371,000 Da之十個窄分散性聚苯乙烯標準品校準。使用Agilent GPC/SEC套裝軟體版本A.02.01 (Build 9.34851)進行資料分析。
NMR光譜法
使用配備有5-mm Prodigy BBO CryoProbe之Bruker Avance III HD 500光譜儀(Billerica, MA)進行NMR光譜法。用10 s的脈衝重複延遲獲得質子光譜。相對於CDCl3之殘餘溶劑質子(δ
1H, 7.26 ppm)報導化學位移。
實例A-用於製備硫化物連接之FTA之一般方法
將GP-71-SS巰基官能性聚矽氧流體（15.0 g，4.5 mmol SH官能基，MW =6600 g/mol，dp =83，針對比較例1及實例1至5）、僅針對實例1之丙烯酸3-(三甲氧基矽基)丙酯(TMSiPA)或針對實例2-5之TMPSiPA與丙烯酸丁酯(BA)或丙烯酸辛酯(OA)之混合物（在所有情況下，總丙烯酸酯官能基為4.5 mmol），以及二甲基苯基膦(6.2 mg, 0.045 mmol)稱重至封蓋之玻璃小瓶中；將頂部空間用氮氣吹掃。將反應混合物藉由渦旋混合器混合30 min，且接著在室溫下保持24 h。隨後將反應混合物藉由重力過濾通過中性氧化鋁塞(2 g)純化。藉由SEC及
1H NMR光譜對產物進行表徵。對於實例6及實例7，使用GP-800巰基官能性聚矽氧流體（15.0 g，9.1 mmol SH官能基，MW = 8400 g/mol，dp=108）及丙烯酸酯之混合物（9.1 mmol丙烯酸酯官能基），以及二甲基苯基膦(0.091 mmol)。
實例B-用於製備胺連接之FTA之一般方法
將GP-6胺基官能性聚矽氧流體（15.0 g，7.5 mmol NH
2官能基，MW =7900 g/mol，dp=100）、針對實例8之TMSiPA (1.8 g，7.5 mmol)或針對實例9之TMSiPA (0.88 g，0.375 mmol)及OA (0.69 g，0.375 mmol)之混合物稱重至封蓋之玻璃小瓶中；將頂部空間用氮氣吹掃。將GP-4胺基官能性聚矽氧流體（15.0 g，12.8 mmol NH
2官能基，MW =4800 g/mol，dp =58）、針對實例10之TMSiPA (1.5 g，6.4 mmol)及OA (1.2 g，6.4 mmol)之混合物稱重至封蓋之玻璃小瓶中；將頂部空間用氮氣吹掃。將反應混合物藉由渦旋混合器混合30 min，且接著在100℃下保持2 h。隨後將反應混合物藉由重力過濾通過中性氧化鋁塞(2 g)純化。藉由SEC及質子NMR光譜對產物進行表徵。表1提供針對比較例1及實例1至10的起始材料及TMPSiPA:BA或TMPSiPA:OA之莫耳比（若適用）的彙總。
表1-FTA樣本之起始材料莫耳比
實例1-10-用於製備具有氧化鋁填料之調配物的通用程序
| 實例編號 | 聚矽氧 | 莫耳比 |
| C1 | GP-71-SS | 僅OA；未添加TMSiPA |
| 1 | 未添加OA或BA | |
| 2 | TMSiPA:OA =3:1 | |
| 3 | TMSiPA:OA =1:1 | |
| 4 | TMSiPA:BA =3:1 | |
| 5 | TMSiPA:BA =1:1 | |
| 6 | GP-800 | TMSiPA:OA =2.86:1 |
| 7 | TMSiPA:OA =0.59:1 | |
| 8 | GP-6 | 未添加OA或BA |
| 9 | TMSiPA: OA =1:1 | |
| 10 | GP-4 | TMSiPA: OA =1:1 |
首先將FTA樣本(0.16 g)及雙乙烯基封端之聚矽氧烷（2.80 g，黏度=60 mP·s）在Max-40混合器杯中以2000 rpm高度混合30 s。接著將此預混合流體(2.96 g)與Al-43-BE氧化鋁粒子(17.02 g)合併且以1300 rpm高速混合30 s。接著將CB-A20S氧化鋁粒子(17.02 g)添加至調配物中且以1300 rpm高速混合30 s。接著將經充分調配的所得熱凝膠手動混合，再次以1300 rpm高速混合30 s，且轉移至玻璃瓶中且在150℃下真空加熱1 h。
擠壓流量之測量
擠壓流量測試用以如下表徵含有FTA之測試調配物樣本的流動性：將導熱測試調配物(0.6 g)夾在兩個玻璃載片（25 ×75 ×1.0 mm，獲自Thermofisher）之間，且由兩個1-mm墊片隔開以控制厚度。手動壓下頂部玻璃載片以確保材料均勻鋪展，且將材料之初始直徑記錄為D
1。接著自測試樣本移除1-mm墊片，且將350-g重物置放於頂部玻璃上且使其靜置1 min。將擠壓後直徑記錄為D
2且該擠壓流量計算為ΔR = (D
2– D
1)/2 (mm)。
0.1%應變下之黏度測量
在測試調配物樣本上進行振盪剪切應變振幅掃描，以表徵調配物黏度及剪切稀化特性。使用25-mm平行板幾何形狀，將測試調配物樣本裝載至Anton Paar高通量流變儀（AP HT流變儀）上。藉由自動修整機以1.0-mm間隙進行修整。在300-s測試前浸泡時間之後，使用10 rad/s振盪頻率之標準程序進行測量，以0.01至300%的應變振幅掃描，每十秒20個取樣點。報導0.1%應變下之黏度（低剪切速率黏度）。
擠出速率之測量
藉由將凝膠調配物裝入30-mL EFD注射器中來量測擠出速率。接著將注射器附接至EFD施配設備且將材料在氮氣下以55 Psi施配5 s。如使用分析天平所判定，擠出速率記錄為在5-s施配時段期間所施配之質量。
導熱率測量
使用Hot Disk暫態平面源工具(TPS 2500S)及Kapton包封的熱探針測量導熱率。在6 mm直徑容器上進行同向性塊體測量。
表2說明熱凝膠樣本之擠壓流量（S.F，以mm為單位）、在0.1%應變下之黏度（Visc.，以Pa·s為單位）、及55 psi下之擠出速率（E.R.，以g/5 s為單位）。
所有FTA均實質上如實例A及實例B中所述製備，不同之處在於改變TMSiPA與BA或TMSiPA與OA之莫耳比。在表2中，TMSiPA
M係指用於製備樣本之TMPSiPA相對於BA或OA之莫耳數的相對莫耳數。類似地，R
2 ' M係指BA或OA相對於TMPSiPA之莫耳數的相對莫耳數。R
5為如所指示之辛基或丁基。DP係指FTA之聚合度。
RMS-759係指DOWSIL
™RMS-759單三甲氧基矽氧基-二甲基矽氧烷聚合物（Dow Chemical Company或其附屬公司之商標），其為比較例2中所使用之FTA。在3.02 W/m·K下測量含有RMS-759之比較凝膠調配物的導熱率；實例調配物的導熱率在2.8與3.0 W/m·K範圍內。無法進行C1之S.F.、Visc.、及E.R.之測量(N.M.)，因為未獲得可流動調配物。
表2-熱凝膠樣本之特性
| 實例編號 | DP | X | TMPSiPA M | R 5 | R 2 ' M | S.F. | Visc. | E.R. |
| C1 | 83 | S | 0 | 正辛基 | 2 | N.M. | N.M. | N.M. |
| 1 | 2 | -- | 0 | 9.5 | 715 | 3.2 | ||
| 2 | 1.5 | 正辛基 | 0.5 | 7.8 | 652 | 3.4 | ||
| 3 | 1 | 正辛基 | 1 | 7.8 | 761 | 3.4 | ||
| 4 | 1.5 | 正丁基 | 0.5 | 7.0 | 1098 | 3.4 | ||
| 5 | 1 | 正丁基 | 1 | 6.3 | 1509 | 3.4 | ||
| 6 | 108 | 4 | 正辛基 | 1.4 | 4.5 | 5619 | 2.8 | |
| 7 | 2 | 正辛基 | 3.4 | 4.8 | 4249 | 2.0 | ||
| 8 | 100 | NH | 4 | -- | 0 | 3.8 | 28200 | 2.1 |
| 9 | 2 | 正辛基 | 2 | 4.5 | 26250 | 1.7 | ||
| 10 | 58 | 2 | 正辛基 | 2 | 3.8 | 18040 | 1.8 | |
| C2 | FTA =RMS-759 | 8.0 | 64.9 | 1.4 |
實例1-10調配物均展現出可接受之擠壓流量、0.1%應變下之黏度、擠出速率、及導熱率。與商業調配物(C2)相比，擠出速率顯著改良，0.1%應變下之黏度亦如此。較高黏度有利於減少組成物中填料之沈降。本發明之調配物亦得益於FTA之易製備性，及調整所關注特性方面的靈活性。
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Claims (8)
- 一種式I之填料處理劑： I 其中m係5至150；n係0.1至5；p係0至5；q係1至6；X係S或NR 6；各R 1獨立地係C 1-C 6烷基、乙烯基、苯基、或苯甲基；各R 1 '獨立地係C 1-C 6烷基； R 2係： R 2'係： 其中R 3係H或甲基；各R 4獨立地係C 1-C 6烷基；a係1至3之整數；R 5係C 1-C 12烷基；R 6係H或C 1-C 6烷基；且虛線表示連接至X之點。
- 如請求項1之填料處理劑，其中各R 1獨立地係C 1-C 6烷基；n係1至3；p係0至2；q係2至4；各R 1獨立地係C 1-C 6烷基；且a係0。
- 如請求項2之填料處理劑，其中各R 1獨立地係甲基或乙基；R 5係甲基、乙基、正丁基、三級丁基、正己基、2-乙基己基、或正辛基；R 3係H；且q係2。
- 如請求項3之填料處理劑，其中各R 1係甲基；R 5係甲基、乙基、正丁基、三級丁基、正己基、2-乙基己基、或正辛基。
- 如請求項4之填料處理劑，其中R 5係正丁基或正辛基；n係2；且p係0。
- 如請求項1至5中任一項之填料處理劑，其中X係S；且m係50至150。
- 如請求項1至5中任一項之填料處理劑，其中X係N；R 6係H；且m係50至150。
- 一種方法，其包含式Ia化合物： 1a 與式Ib之丙烯酸酯或甲基丙烯酸酯： 1b 及可選地，式Ic之丙烯酸酯或甲基丙烯酸酯： 1c 在偶合催化劑存在下接觸以形成式I化合物： I 其中m係5至150；n係0.1至5；p係0至5；q係1至6；X係S或NR 6；各R 1獨立地係C 1-C 6烷基、乙烯基、苯基、或苯甲基；各R '獨立地係C 1-C 6烷基； R 2係： R 2'係： 其中R 3係H或甲基；各R 4獨立地係C 1-C 6烷基；a係1至3之整數；R 5係C 1-C 12烷基，R 6係H或C 1-C 6烷基，且虛線表示連接至X之點。
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| JP3224862B2 (ja) * | 1992-06-25 | 2001-11-05 | 東レ・ダウコーニング・シリコーン株式会社 | アミノ基含有オルガノポリシロキサンおよびその製造方法 |
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