公开(公告)号：US20060211834A1

公开(公告)日：2006-09-21

申请号：US10519228

申请日：2003-06-26

Applicant: Tomoo Sugawara

Inventor： Tomoo Sugawara

IPC: C08F136/00

CPC classification number: B32B27/08 ,  B32B15/08 ,  B32B27/06 ,  B32B27/18 ,  B32B2398/20 ,  B32B2457/08 ,  C08G61/08 ,  C08J5/18 ,  C08J2365/00 ,  Y10S526/902 ,  Y10T428/2915 ,  Y10T428/2971 ,  Y10T428/31678

Abstract: The invention relates to a process for the production of post-crosslinkable thermoplastic resins by bulk-polymerizing a polymerizable composition (A) comprising (I) a monomer fluid containing a cyclic olefin (α) having two or more metathetical ring-opening reaction sites in the molecule in an amount 10 wt % or above based on the total amount of the monomers or a monomer fluid containing a norbornene monomer and a crosslinking agent, (II) a metathetical polymerization catalyst, and (III) a chain transfer agent; thermoplastic resins obtained by this process; and a process for producing crosslinked resins or crosslinked resin composite materials which comprises laminating such a thermoplastic resin with a substrate at need and then crosslinking the thermoplastic resin. According to the invention, thermoplastic resins which are free from odor due to residual monomers and excellent in storage stability can be efficiently obtained by a simple process of bulk-polymerizing the composition (A). The process is not only easy and simple but also applicable to continuous production, thus being industrially advantageous. The crosslinked resins and crosslinked resin composite materials obtained according to the invention are excellent in electrical insulation properties, mechanical strengths, heat resistance, dielectric characteristics and so on, thus being useful as electrical materials or the like.

公开(公告)号：US5204427A

公开(公告)日：1993-04-20

申请号：US708079

申请日：1991-05-24

Applicant: Masao Torii ,  Tomoo Sugawara ,  Kin-ichi Okumura ,  Motoyuki Yamato

Inventor： Masao Torii ,  Tomoo Sugawara ,  Kin-ichi Okumura ,  Motoyuki Yamato

IPC: C08G61/08

CPC classification number: C08G61/08 ,  Y10S526/902

Abstract: A reaction solution comprising a mixture of tricyclopentadiene, a norbornene monomer with at least 3 rings in its backbone, a 5-alkenyl-2-norbornene pot life adjusting agent along with a molybdenum type catalyst system gives prolonged pot life without extending time to exotherm (e.g., smoking time). By utilizing this reaction solution it is possible to bulk polymerize reinforced or unreinforced articles in a mold via ring-opening polymerization. Articles so obtained have good outward appearance and excellent physical properties.

Abstract translation: 包含三环戊二烯，其主链中具有至少3个环的降冰片烯单体，5-链烯基-2-降冰片烯适用期调节剂以及钼型催化剂体系的混合物的反应溶液具有延长的使用期，而不延长放热时间 例如吸烟时间）。 通过利用该反应溶液，可以通过开环聚合在模具中大量聚合增强或未增强的制品。 所得物品外观好，物理性能优良。

公开(公告)号：US07771834B2

公开(公告)日：2010-08-10

申请号：US12236837

申请日：2008-09-24

Applicant: Tomoo Sugawara

Inventor： Tomoo Sugawara

IPC: B32B15/08 ,  C08G61/12 ,  B32B37/00

CPC classification number: B32B27/08 ,  B32B15/08 ,  B32B27/06 ,  B32B27/18 ,  B32B2398/20 ,  B32B2457/08 ,  C08G61/08 ,  C08J5/18 ,  C08J2365/00 ,  Y10S526/902 ,  Y10T428/2915 ,  Y10T428/2971 ,  Y10T428/31678

Abstract: Process for production of post-crosslinkable thermoplastic resins by bulk-polymerizing a polymerizable composition (A) comprising (I) a monomer fluid containing a cyclic olefin (α) having two or more metathetical ring-opening reaction sites in the molecule in an amount 10 wt % or above based on the total amount of the monomers or a monomer fluid containing a norbornene monomer and a crosslinking agent, (II) a metathetical polymerization catalyst, and (III) a chain transfer agent; thermoplastic resins obtained by this process. These thermoplastic resins are free from odor due to residual monomers and are excellent in storage stability. Process for producing crosslinked resins and composite materials which comprises laminating the thermoplastic resin to a substrate and then crosslinking the thermoplastic resin. These crosslinked resins and composite materials are invention are excellent in electrical insulation properties, mechanical strength, heat resistance, and dielectric characteristics, and are useful as electrical materials.

Abstract translation: 通过使聚合性组合物（A）进行本体聚合来制造后交联性热塑性树脂的方法，其包含（I）含有分子中具有两个以上元素开环反应位点的环状烯烃（α）的单体流体，其量为10 基于单体或含有降冰片烯单体和交联剂的单体流体的总量，（II）微量聚合催化剂和（III）链转移剂的总重量％以上。 通过该方法获得的热塑性树脂。 这些热塑性树脂由于残留单体而没有气味，并且储存稳定性优异。 制造交联树脂和复合材料的方法，其包括将热塑性树脂层压到基底上，然后交联热塑性树脂。 这些交联树脂和复合材料本身具有优异的电绝缘性，机械强度，耐热性和介电特性，并且可用作电气材料。

公开(公告)号：US20070191563A1

公开(公告)日：2007-08-16

申请号：US11783705

申请日：2007-04-11

Applicant: Tomoo Sugawara

Inventor： Tomoo Sugawara

IPC: C08F136/00

CPC classification number: B32B27/08 ,  B32B15/08 ,  B32B27/06 ,  B32B27/18 ,  B32B2398/20 ,  B32B2457/08 ,  C08G61/08 ,  C08J5/18 ,  C08J2365/00 ,  Y10S526/902 ,  Y10T428/2915 ,  Y10T428/2971 ,  Y10T428/31678

Abstract: The invention relates to a process for the production of post-crosslinkable thermoplastic resins by bulk-polymerizing a polymerizable composition (A) comprising (I) a monomer fluid containing a cyclic olefin (α) having two or more metathetical ring-opening reaction sites in the molecule in an amount 10 wt % or above based on the total amount of the monomers or a monomer fluid containing a norbornene monomer and a crosslinking agent, (II) a metathetical polymerization catalyst, and (III) a chain transfer agent; thermoplastic resins obtained by this process; and a process for producing crosslinked resins or crosslinked resin composite materials which comprises laminating such a thermoplastic resin with a substrate at need and then crosslinking the thermoplastic resin. According to the invention, thermoplastic resins which are free from odor due to residual monomers and excellent in storage stability can be efficiently obtained by a simple process of bulk-polymerizing the composition (A). The process is not only easy and simple but also applicable to continuous production, thus being industrially advantageous. The crosslinked resins and crosslinked resin composite materials obtained according to the invention are excellent in electrical insulation properties, mechanical strengths, heat resistance, dielectric characteristics and so on, thus being useful as electrical materials or the like.

Abstract translation: 本发明涉及一种通过使聚合性组合物（A）进行本体聚合来制备后交联性热塑性树脂的方法，所述聚合性组合物（A）包含（I）含有具有两个以上元素开环反应位点的环状烯烃（α）的单体流体， 基于单体或含有降冰片烯单体和交联剂的单体流体的总量，（II）微分聚合催化剂和（III）链转移剂的量的10重量％以上的分子; 通过该方法获得的热塑性树脂; 以及用于生产交联树脂或交联树脂复合材料的方法，其包括在需要时将这种热塑性树脂与基底层压，然后交联热塑性树脂。 根据本发明，通过本体聚合组合物（A）的简单方法可以有效地获得由于残留单体而没有气味并且储存稳定性优异的热塑性树脂。 该方法不仅容易和简单，而且适用于连续生产，在工业上具有优势。 根据本发明获得的交联树脂和交联树脂复合材料具有优异的电绝缘性能，机械强度，耐热性，介电特性等，因此可用作电气材料等。

公开(公告)号：US20070037946A1

公开(公告)日：2007-02-15

申请号：US10544005

申请日：2004-02-02

Applicant: Tomoo Sugawara

Inventor： Tomoo Sugawara

IPC: C08F36/00

CPC classification number: C08J5/24 ,  C08G61/02 ,  C08G61/08 ,  C08J5/18 ,  C08J2365/00 ,  Y10T428/31645

Abstract: A process (1) for producing a cycloolefin resin film comprising the steps of: the step (I) of mixing a cycloolefin monomer and a metathesis polymerization catalyst to prepare a polymerizable composition (A); the step (II) of coating or impregnating the supporting body with the polymerizable composition (A) at once after the step (I), and the step (III) of polymerizing the polymerizable composition (A) by polymerization; and a process (2) for producing a cycloolefin polymer sheet or film with the thickness of 1 mm or less comprising polymerizing a reactive solution containing a ruthenium complex catalyst, having a hetero atom-containing carbene compound as a ligand, and a cycloolefin monomer by ring-opening metathesis bulk polymerization, wherein the polymerization of the cycloolefin monomer is completed by heating the reactive solution to 100° C. or higher at the heating rate of 20° C./min or more. Thus, a cycloolefin resin film having excellent adhesion to other materials and a cycloolefin polymer sheet or film having a thickness of 1 mm or can be efficiently produced.

Abstract translation: 一种制备环烯烃树脂膜的方法（1），包括以下步骤：将环烯烃单体和易位聚合催化剂混合以制备可聚合组合物（A）的步骤（I）; 在步骤（I）之后立即用可聚合组合物（A）涂覆或浸渍支撑体的步骤（II）和通过聚合聚合可聚合组合物（A）的步骤（III）; 以及用于制造厚度为1mm以下的环烯烃聚合物片材或膜的方法（2），包括使含有含杂原子的卡宾化合物作为配体的含有钌络合物催化剂的反应性溶液和环烯烃单体聚合， 开环复分解本体聚合，其中环烯烃单体的聚合通过以20℃/分钟以上的加热速率将反应溶液加热至100℃或更高来完成。 因此，与其它材料的密合性优异的环烯烃树脂膜和厚度为1mm的环烯烃聚合物片材或膜可以有效地制造。

公开(公告)号：US5063103A

公开(公告)日：1991-11-05

申请号：US367580

申请日：1989-06-19

Applicant: Tomoo Sugawara ,  Motoyuki Yamato

Inventor： Tomoo Sugawara ,  Motoyuki Yamato

IPC: C08G61/08 ,  C08J5/08 ,  C08L65/00

CPC classification number: C08J5/08 ,  C08G61/08 ,  C08L65/00 ,  C08J2365/00 ,  Y10T428/2947 ,  Y10T442/2992

Abstract: A reinforced polymeric matrix comprising a glass mat and a norbornene polymer surrounding the glass mat, the glass mat is composed of at least one glass fiber treated with a silane coupling agent and a binder adhering the glass fiber(s) to the norbornene polymer; the binder is selected from polyolefins, vinyl aromatic polymers, and ring-opened polymers of at least one norbornene-type monomer containing at least one norbornene group. Process for making a reinforced polymeric matrix comprises positioning a glass mat within a mold, the glass mat having been treated with a hydrocarbon polymer binder; mixing a plurality of streams, one stream containing a catalyst of a metathesis catalyst system, another stream containing a cocatalyst of a metathesis system, and at least one of the streams containing at least one norbornene-type monomer which is liquid at room temperature to form a mixed stream; introducing the mixed stream into the mold around the mat; polymerizing by ring opening the monomer(s) in the mold; and extracting from the mold the reinforced polymeric matrix, wherein the norbornene polymer is thermoset.

公开(公告)号：US07803870B2

公开(公告)日：2010-09-28

申请号：US12499433

申请日：2009-07-08

Applicant: Tomoo Sugawara

Inventor： Tomoo Sugawara

IPC: C08G61/08 ,  C08F2/44 ,  C08K5/49

CPC classification number: C08G61/08 ,  C08K5/0066

Abstract: Disclosed are a cycloolefin resin molded product having excellent flame retardance and a polymerizable composition used for producing such a molded product. A polymerizable composition comprising the cycloolefin monomer, a flame retardant and a metathesis polymerization catalyst is characterized in that a monomer having a condensed ring formed of an aliphatic ring having one or more carbon-carbon double bonds and a ring with aromatic characteristics is used as the cycloolefin monomer. A molded product can be produced through bulk polymerization of this polymerizable composition.

Abstract translation: 公开了具有优异阻燃性的环烯烃树脂模塑制品和用于生产这种模制产品的可聚合组合物。 包含环烯烃单体，阻燃剂和易位聚合催化剂的可聚合组合物的特征在于，使用由具有一个或多个碳 - 碳双键的脂族环和具有芳香特性的环形成的稠环的单体作为 环烯烃单体。 可以通过该可聚合组合物的本体聚合来制备模制产品。

公开(公告)号：US07579404B2

公开(公告)日：2009-08-25

申请号：US10567257

申请日：2004-08-09

Applicant: Tomoo Sugawara

Inventor： Tomoo Sugawara

IPC: C08L45/00 ,  C08K5/49 ,  C08F2/44

CPC classification number: C08G61/08 ,  C08K5/0066

Abstract: Disclosed are a cycloolefin resin molded product having excellent flame retardance and a polymerizable composition used for producing such a molded-product. A polymerizable composition comprising the cycloolefin monomer, a flame retardant and a metathesis polymerization catalyst is characterized in that a monomer having a condensed ring formed of an aliphatic ring having one or more carbon-carbon double bonds and a ring with aromatic characteristics is used as the cycloolefin monomer. A molded product can be produced through bulk polymerization of this polymerizable composition.

Abstract translation: 公开了具有优异阻燃性的环烯烃树脂模塑制品和用于制备这种模制产品的可聚合组合物。 包含环烯烃单体，阻燃剂和易位聚合催化剂的可聚合组合物的特征在于，使用由具有一个或多个碳 - 碳双键的脂族环和具有芳香特性的环形成的稠环的单体作为 环烯烃单体。 可以通过该可聚合组合物的本体聚合来制备模制产品。

公开(公告)号：US20060293444A1

公开(公告)日：2006-12-28

申请号：US10567257

申请日：2004-08-09

Applicant: Tomoo Sugawara

Inventor： Tomoo Sugawara

IPC: C08K5/49

CPC classification number: C08G61/08 ,  C08K5/0066

Abstract: Disclosed are a cycloolefin resin molded product having excellent flame retardance and a polymerizable composition used for producing such a molded-product. A polymerizable composition comprising the cycloolefin monomer, a flame retardant and a metathesis polymerization catalyst is characterized in that a monomer having a condensed ring formed of an aliphatic ring having one or more carbon-carbon double bonds and a ring with aromatic characteristics is used as the cycloolefin monomer. A molded product can be produced through bulk polymerization of this polymerizable composition.

公开(公告)号：US5463002A

公开(公告)日：1995-10-31

申请号：US951597

申请日：1992-09-28

Applicant: Tomoo Sugawara ,  Shingo Kudo ,  Kin-ichi Okumura

Inventor： Tomoo Sugawara ,  Shingo Kudo ,  Kin-ichi Okumura

IPC: B01J31/14 ,  C08G61/06 ,  C08G61/08 ,  C08F4/52

CPC classification number: C08G61/08 ,  Y10S526/902

Abstract: A halogenated aluminum-based cocatalyst provides a metathesis catalyst system with high activity, moisture insensitivity, and long pot lives. The cocatalyst can be employed in solution or in in-mold bulk polymerization processes.

Abstract translation: 卤化铝基助催化剂提供了具有高活性，不敏感性和长使用寿命的复分解催化剂体系。 助催化剂可用于溶液或模内本体聚合方法。