Metathesis polymerization

Claim 2

A process for producing a cross-linked polymer, which comprises polymerizing at least one of metathesis polymerizable monomers in the presence of a metathesis polymerization catalyst system and at least one of (a) carboxylic acid halides, (b) carboxylic acid anhydrides, (c) organic halogenated silicon compounds having at least one halogen-silicon bond, (d) halogenated phosphorus compounds having at least one halogen-phosphorus bond and (e) halogenated sulfur compounds having at least one halogen-­sulfur bond.

Claim 3

A process of claim 1 in which the metathesis polymerization catalyst system comprises a catalyst component containing at least one of transition metals and an activator component.

Claim 4

A process of claim 2 in which at least one of the compounds (a), (b), (c), (d) and (e) are used in the amount of 0.3-4 equivalent of carboxylic acid halides, carboxylic acid anhydrides, halogenated silicon atom of said (c), halogenated phosphorus atom of said (d) or halogenated sulfur atom of (e) per 1 equivalent atom of the transition metal in the catalyst component.

Claim 5

A process of claim 1, 2 or 3 in which the compounds (a) are aliphatic carboxylic acid chlorides, aromatic carboxylic acid chlorides or their mixture, the compounds (b) are aliphatic carboxylic acid anhydrides, aromatic acid anhydrides or their mixture, the compounds (c) are organic halogenated silanes, organic halogenated siloxanes or their mixture, the compounds (d) are halogenated phosphorus compounds having the formula P(R)a(X)b or PO(R)aʹ(X)bʹ wherein R is an organic group, X is a halogen atom, a is an integer of 0-3, b is an integer of 1-5, the sum of a and b is 3 or 5, aʹ is an integer of 0-2, bʹ is an integer of 1-3, and the sum of aʹ and bʹ is 3, halogen-containing esters of said halogenated phosphorus compounds, partially-hydrolyzed and condensed halogen-containing products of said halogenated compounds or their mixture and the compounds (e) are halides of sulfur-containing oxyacids, sulfur halides, halides of mercaptans or their mixture.

Claim 6

A process of claim 1 or claims 2 to 4 in which the compounds (a), (b), (c), (d) and (e) have a boiling point of at least 60°C and are soluble in the metathesis polymerizable monomers.

Claim 7

A process of claim 1 or claims 2 to 5 in which the metathesis polymerizable monomers comprise dicyclopentadiene or a mixture of dicyclopentadiene and at least one of other monomers.

Claim 8

A cross-linked polymer produced by the process of claim 1, or claims 2 to 6.

Claim 9

A process for producing a molded article by introducing a reactive liquid mixture into a mold in which said liquid mixture is metathesis polymerized in bulk to produce the molded article, said liquid mixture comprising at least one of metathesis polymerizable monomers, a metathesis polymerization catalyst system and at least one of (a) carboxylic acid halides, (b) carboxylic acid anhydride, (c) organic halogenated silicon compounds having at least one halogen-silicon bond, (d) halogenated phosphorus compounds having at least one halogen-phosphorus bond and (e) halogenated sulfur compounds having at least one halogen-­sulfur bond.

Claim 10

A process for producing a molded article by introducing a reactive liquid mixture into a mold in which said liquid mixture is metathesis polymerized in bulk to produce the molded article, said liquid mixture comprising at least one of metathesis polymerizable monomers, a metathesis polymerization catalyst system and at least one of (a) carboxylic acid halides, (b) carboxylic acid anhydride, (c) organic halogenated silicon compounds having at least one halogen-silicon bond, (d) halogenated phosphorus compounds having at least one halogen-phosphorus bond and (e) halogenated sulfur compounds having at least one halogen-­sulfur bond.

Claim 11

A process of claim 8 in which the metathesis polymerization catalyst system comprises a catalyst component containing at least one of transition metals and an activator component.

Claim 12

A process of claim 9 in which at least one of the compounds (a), (b), (c), (d) and (e) are used in the amount of 0.3-4 equivalent of carboxylic acid halides, carboxylic acid anhydrides, halogenated silicon atom of said (c), halogenated phosphorus atom of said (d) or halogenated sulfur atom of (e) per 1 equivalent atom of the transition metal in the catalyst component.

Claim 13

A process of claim 8, 9 or 10 in which the compounds (a) are aliphatic carboxylic acid chlorides, aromatic carboxylic acid chlorides or their mixture, the compounds (b) are aliphatic carboxylic acid anhydrides, aromatic acid anhydrides or their mixture, the compounds (c) are organic halogenated silanes, organic halogenated siloxanes or their mixture, the compounds (d) are halogenated phosphorus compounds having the formula P(R)a(X)b or PO(R)aʹ(X)bʹ wherein R is an organic group, X is a halogen atom, a is an integer of 0-3, b is an integer of 1-5, the sum of a and b is 3 or 5, and aʹ is an integer of 0-2, bʹ is an integer of 1-3, and the sum of aʹ and bʹ is 3, halogen-containing esters of said halogenated phosphorus compounds, partially-hydrolyzed and condensed halogen-containing products of said halogenated compounds or their mixture and the compounds (e) are halides of sulfur-containing oxyacids, sulfur halides, halides of mercaptans or their mixture.

Claim 14

A process of claim 8 or claims 9 to 11 in which the compounds (a), (b), (c), (d) and (e) have a boiling point of at least 60°C and are soluble in the metathesis polymerizable monomers.

Claim 15

A process of claim 8 or claims 9 to 12 in which the metathesis polymerizable monomers comprise dicyclopentadiene or a mixture of dicyclopentadiene and at least one of other monomers.

Claim 16

A molded article produced by the process of claim 8 or claims 9 to 13.

Claim 17

A multi-part polymerizable composition which comprises at least one of metathesis polymerizable monomers, a metathesis polymerization catalyst system and at least one of (a) carboxylic acid halides, (b) carboxylic acid anhydridies, (c) organic halogenated silicon compounds having at least one halogen-silicon bond, (d) halogenated phosphorus compounds having at least one halogen-phosphorus bond and (e) halogenated sulfur compounds having at least one halogen-­sulfur bond, and said metathesis polymerization catalyst system comprising a catalyst component and an activator component which are not present in the same parts.

Claim 18

A multi-part polymerizable composition which comprises at least one of metathesis polymerizable monomers, a metathesis polymerization catalyst system and at least one of (a) carboxylic acid halides, (b) carboxylic acid anhydridies, (c) organic halogenated silicon compounds having at least one halogen-silicon bond, (d) halogenated phosphorus compounds having at least one halogen-phosphorus bond and (e) halogenated sulfur compounds having at least one halogen-­sulfur bond, and said metathesis polymerization catalyst system comprising a catalyst component and an activator component which are not present in the same parts.

Claim 19

A composition of claim 15 in which the catalyst component contains at least one of transition metals.

Claim 20

A composition of claim 16 in which at least one of the compounds (a), (b), (c), (d) and (e) are used in the amount of 0.3-4 equivalent of carboxylic acid halides, carboxylic acid anhydrides, halogenated silicon atom of said (c), halogenated phosphorus atom of said (d) or halogenated sulfur atom of (e) per 1 equivalent atom of the transition metal in the catalyst component.

Claim 21

A composition of claim 15, 16 or 17 in which the compounds (a) are aiiphatic carboxylic acid chlorides, aromatic carboxylic acid chlorides or their mixture, the compounds (b) are aliphatic carboxylic acid anhydrides, aromatic acid anhydrides or their mixture, the compounds (c) are organic halogenated silanes, organic halogenated siloxanes or their mixture, the compounds (d) are halogenated phosphorus compounds having the formula P(R)a(X)b or PO(R)aʹ(X)bʹ wherein R is an organic group, X is a halogen atom, a is an integer of 0-3, b is an integer of 1-5, the sum of a and b is 3 or 5, and aʹ is an integer of 0-2, bʹ is an integer of 1-3, and the sum of aʹ and bʹ is 3, halogen-containing esters of said halogenated phosphorus compounds, partially-hydrolyzed and condensed halogen-containing products of said halogenated compounds or their mixture and the compounds (e) are halides of sulfur-containing oxyacids, sulfur halides, halides of mercaptans or their mixture.

Claim 22

A composition of claim 15 or claims 16 to 18 in which the compounds (a), (b), (c), (d) and (e) have a boiling point of at least 60°C and are soluble in the metathesis polymerizable monomers.

Claim 23

A composition of claim 15 or claims 16 to 19 in which the metathesis polymerizable monomers comprise dicyclopentadiene or a mixture of dicyclopentadiene and at least one of other monomers.

Claim 24

Use of the compositions of claims 15 to 20 for the preparation of molded articles.

Claim 25

A process of claims 1 to 13 for the preparation of molded articles.