JP6676375B2 - 耐熱性炭化水素エラストマー組成物 - Google Patents
耐熱性炭化水素エラストマー組成物 Download PDFInfo
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- JP6676375B2 JP6676375B2 JP2015545795A JP2015545795A JP6676375B2 JP 6676375 B2 JP6676375 B2 JP 6676375B2 JP 2015545795 A JP2015545795 A JP 2015545795A JP 2015545795 A JP2015545795 A JP 2015545795A JP 6676375 B2 JP6676375 B2 JP 6676375B2
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- polyamide
- ethylene copolymer
- blend
- phr
- rubber
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- PZWQRDVVVKIYLX-UHFFFAOYSA-N bicyclo[3.2.0]hepta-2,6-diene Chemical compound C1C=CC2C=CC12 PZWQRDVVVKIYLX-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229920006038 crystalline resin Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- VDBXLXRWMYNMHL-UHFFFAOYSA-N decanediamide Chemical compound NC(=O)CCCCCCCCC(N)=O VDBXLXRWMYNMHL-UHFFFAOYSA-N 0.000 description 1
- YWJUZWOHLHBWQY-UHFFFAOYSA-N decanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCC(O)=O YWJUZWOHLHBWQY-UHFFFAOYSA-N 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 150000001990 dicarboxylic acid derivatives Chemical class 0.000 description 1
- QFTYSVGGYOXFRQ-UHFFFAOYSA-N dodecane-1,12-diamine Chemical compound NCCCCCCCCCCCCN QFTYSVGGYOXFRQ-UHFFFAOYSA-N 0.000 description 1
- ZMUCVNSKULGPQG-UHFFFAOYSA-N dodecanedioic acid;hexane-1,6-diamine Chemical compound NCCCCCCN.OC(=O)CCCCCCCCCCC(O)=O ZMUCVNSKULGPQG-UHFFFAOYSA-N 0.000 description 1
- 239000003623 enhancer Substances 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- 229920006168 hydrated nitrile rubber Polymers 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- HRRDCWDFRIJIQZ-UHFFFAOYSA-N naphthalene-1,8-dicarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=CC2=C1 HRRDCWDFRIJIQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- FJXWKBZRTWEWBJ-UHFFFAOYSA-N nonanediamide Chemical compound NC(=O)CCCCCCCC(N)=O FJXWKBZRTWEWBJ-UHFFFAOYSA-N 0.000 description 1
- 125000003518 norbornenyl group Chemical class C12(C=CC(CC1)C2)* 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229920000933 poly (ε-caprolactam) Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000010074 rubber mixing Methods 0.000 description 1
- 238000010057 rubber processing Methods 0.000 description 1
- 229910052604 silicate mineral Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 229920001897 terpolymer Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/083—Copolymers of ethene with aliphatic polyenes, i.e. containing more than one unsaturated bond
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
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- Compositions Of Macromolecular Compounds (AREA)
Description
ECP1 Nordel(登録商標)3720P、69重量%のエチレン、30.5%のプロピレンおよび0.5%のエチリデンノルボルネンの組成であり、20のMooney粘度(ML1+4、125℃)のThe Dow Chemical Companyから入手可能なエチレンコポリマーエラストマー。
Mooney粘度:ASTM D1646、ML 1+4、125℃
硬化応答:ASTM D5289−07aに従って、0.5°アークで操作される、Alpha TechnologiesからのMDR 2000を使用して測定する。180℃の試験条件を10分間。MLは、試験の間に測定される最小トルク値を指し、MHは、MLの後に達成される最大トルク値を指す。
ポリアミドPA1およびエチレンコポリマーエラストマーECP1の2種のブレンドは、表1の調製に従って製造した。ブレンドB1は相溶化剤C1を含んでなるが、ブレンドB2は含まない。ブレンドは、(ポリアミドPA1の溶融ピーク温度より20℃高い)240℃の設定温度および約30rpmのローター速度で操作されるローラーブレードを備えたHaake(登録商標)Rheocordミキシングボウルにポリマーを充填することによって製造した。ミキシングボウルが完全に充填されたら、ローター速度を100rpmに増加した。ポリマーブレンド溶融温度を監視し、そしてポリマーブレンド温度が220℃(ポリアミドの溶融ピーク温度)に達した時にタイマーを始動した。同時に、ボウル温度の設定点をポリアミドの溶融ピーク温度に適合させるために低下させ、そしてボウルの空冷を開始した。3分の混合後、ローターを停止し、この時点でポリマーブレンドの温度は、ポリアミドの溶融ピーク温度より10℃〜25℃高い範囲にあった。ブレンドをボウルから取り出し、そしてさらなる加工の前に、室温(約25℃)まで冷却した。
ブレンドB3〜B5は、表3の調製物に従って、ECP2およびPA2、PA3またはPA4を使用して製造された。ブレンドは、ブレンド中のポリアミドの溶融ピーク温度より20℃高い設定温度および約30rpmのローター速度で操作されるローラーブレードを備えたHaake(登録商標)Rheocordミキシングボウルにポリマーを充填することによって製造した。ミキシングボウルが完全に充填されたら、ローター速度を100rpmに増加した。ポリマーブレンド溶融温度を監視し、そしてポリマーブレンド温度がポリアミドの溶融ピーク温度に達した時にタイマーを始動した。同時に、ボウル温度の設定点をポリアミドの溶融ピーク温度に適合させるために低下させ、そしてボウルの空冷を開始した。3分の混合後、ローターを停止し、この時点でポリマーブレンドの温度は、ポリアミドの溶融ピーク温度より10℃〜25℃高い範囲にあった。ブレンドをボウルから取り出し、そしてさらなる加工の前に、室温(約25℃)まで冷却した。
本発明は以下の実施の態様を含むものである。
1. (a)エチレンコポリマーエラストマーと、
(b)ASTM D3418−08に従って測定する場合に約160℃またはそれより高い溶融ピーク温度を有し、温風老化を改善するために少なくとも有効な量で存在するが、5phrより多くないポリアミドと、
(c)硬化剤と、
(d)任意選択的に相溶化剤と
を含んでなる硬化性エラストマー組成物。
2. 前記エチレンコポリマーエラストマーが、(i)エチレン含有量が約75重量%またはそれ未満である、エチレンとアルファ−オレフィンとの共重合単位を含んでなる、前記1に記載の組成物。
3. 前記ポリアミドが0.1phr〜5phrの濃度(level)で存在する、前記1に記載の組成物。
4. 前記ポリアミドが0.5phr〜4phrのポリアミドの濃度で存在する、前記1に記載の組成物。
5. 前記ポリアミドが1phr〜3phrのポリアミドの濃度で存在する、前記1に記載の組成物。
6. 前記ポリアミドが、ナイロン6、ナイロン6/6および約270℃未満の溶融ピーク温度を有するグループIVポリアミドからなる群から選択される、前記1に記載の組成物。
7. 前記ポリアミドが、ナイロン6、ナイロン6/6からなる群から選択される、前記6に記載の組成物。
8. 相溶化剤が存在する、前記1に記載の組成物。
9. 前記相溶化剤(i)が、エチレンおよびアミンまたは酸反応性部分を含んでなるポリマーである、前記8に記載の組成物。
10. 前記相溶化剤が、無水マレイン酸グラフト化エチレンアルファ−オレフィンである、前記8に記載の組成物。
11. 前記硬化剤がペルオキシド硬化剤である、前記1に記載の組成物。
12. 前記組成物が、10分間、0.5°アークおよび180℃の試験条件を使用して、ASTM D5289−07aに従って測定する場合、少なくとも2.5dN−mの硬化応答MH−MLを有する、前記1に記載の組成物。
13. (i)前記ポリアミドの溶融ピーク温度より高い温度で混合することによって、エチレンコポリマーエラストマーゴム中に前記ポリアミドを分散し、ブレンドを提供するステップと、
(ii)任意選択的に相溶化剤を添加するステップと、
(iii)前記ブレンドが約200未満のMooney粘度(ML 1+4、125℃)を有するように、前記ポリアミドの結晶化ピーク温度未満まで前記ブレンドを冷却するステップと、
(iv)必要に応じて前記(iii)からのブレンドに同一または異なるエチレンコポリマーエラストマーゴムを任意選択的に混合して、約5phrまたはそれ未満のポリアミドを含んでなる、ポリアミドとエチレンコポリマーとのブレンドを製造するステップと、
(v)前記ポリアミドの溶融ピーク温度未満の温度で、約5phrまたはそれ未満のポリアミドを含んでなる前記ブレンドに硬化剤を添加するステップと
を含んでなる、前記1に記載の硬化性組成物の製造方法。
14. 前記ポリアミドのピーク溶融温度未満の温度で、前記ブレンドを、追加の充填剤、酸化防止剤、加工助剤、可塑剤、ワックス、剥離助剤、酸捕捉剤、着色剤および特性向上剤(property enhancer)からなる群から選択される添加剤と混合する工程をさらに含んでなる、前記13に記載の方法。
15. 前記硬化剤がペルオキシド硬化剤である、前記13に記載の方法。
16. 前記硬化性組成物を所望の物品に成形し、前記組成物を硬化する工程をさらに含んでなる、前記13に記載の方法。
17. 前記成形物品が、ワイヤージャケット、ケーブルジャケット、成形もしくは押出成形チュービングまたはホース、あるいは成形ブート、ベルト、グロメット、シールおよびガスケットからなる群から選択される、前記16に記載の方法。
Claims (2)
- (a)エチレンコポリマーエラストマーと、
(b)ASTM D3418−08に従って測定する場合に160℃またはそれより高い溶融ピーク温度を有し、温風老化を改善するために少なくとも有効な量で存在するが、5phrより多くない完全脂肪族ポリアミドと、
(c)硬化剤と、
を含むが、相溶化剤を含まない、硬化性エラストマー組成物。 - (i)前記ポリアミドの溶融ピーク温度より高い温度で混合することによって、エチレンコポリマーエラストマーゴム中に前記ポリアミドを分散し、ブレンドを提供するステップと、
(iii)前記ブレンドが200未満のMooney粘度(ML 1+4、125℃)を有するように、前記ポリアミドの結晶化ピーク温度未満まで前記ブレンドを冷却するステップと、
(iv)必要に応じて前記(iii)からのブレンドに同一または異なるエチレンコポリマーエラストマーゴムを任意選択的に混合して、5phrまたはそれ未満のポリアミドを含んでなる、ポリアミドとエチレンコポリマーとのブレンドを製造するステップと、
(v)前記ポリアミドの溶融ピーク温度未満の温度で、5phrまたはそれ未満のポリアミドを含んでなる前記ブレンドに硬化剤を添加するステップと
を含んでなる、請求項1に記載の硬化性組成物の製造方法。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201261733086P | 2012-12-04 | 2012-12-04 | |
US61/733,086 | 2012-12-04 | ||
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JP2017519087A (ja) * | 2014-07-04 | 2017-07-13 | ディーエスエム アイピー アセッツ ビー.ブイ. | 太陽電池モジュール用の単層バックシート |
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DE112019006611B4 (de) * | 2019-01-09 | 2023-12-07 | Toyota Boshoku Kabushiki Kaisha | Verwendung eines Materials als schwingungsabsorbierendes Material |
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