CN106905482B - A kind of polymerizable composition, polymerizable composition and its composite material and preparation method - Google Patents
A kind of polymerizable composition, polymerizable composition and its composite material and preparation method Download PDFInfo
- Publication number
- CN106905482B CN106905482B CN201510981717.3A CN201510981717A CN106905482B CN 106905482 B CN106905482 B CN 106905482B CN 201510981717 A CN201510981717 A CN 201510981717A CN 106905482 B CN106905482 B CN 106905482B
- Authority
- CN
- China
- Prior art keywords
- polymerizable composition
- composite material
- cycloolefin
- glass fibre
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/08—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F132/00—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F132/08—Homopolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having condensed rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F232/00—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F232/02—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings
- C08F232/06—Copolymers of cyclic compounds containing no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having no condensed rings having two or more carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/72—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44
- C08F4/80—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from metals not provided for in group C08F4/44 selected from iron group metals or platinum group metals
-
- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L47/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention discloses a kind of polymerizable composition, polymerizable compositions, the composition contains cycloolefin, metathesis polymerization catalyst and glass fibre, cycloolefin relative to 100 parts by weight, the content of the glass fibre is 4-40 parts by weight, the content of the metathesis polymerization catalyst is 0.1-1 parts by weight, wherein, the length of the glass fibre is 1.2-15mm.The invention also discloses the composite material obtained by above-mentioned polymerizable composition, polymerizable composition ring-opening polymerisation with and preparation method thereof.The heat resistance and tensile property of the composite material that polymerization obtains can be improved by the way that the glass fibre that length is 1.2-15mm is added in cycloolefin monomers in the present invention, and composite material can be made under relatively mild conditions, reduce the production cost of composite material.
Description
Technical field
The present invention relates to cycloolefin field of compound material, and in particular, to a kind of polymerism of cycloolefin and glass fibre
Composition and its composite material.
Background technique
Cycloolefin polymer is that one kind is obtained by cycloolefins such as cyclopentadiene, norbornene through ring opening metathesis polymerization
The engineering plastics with high added value.Wherein polydicyclopentadiene is by monomer dicyclopentadiene
One kind obtained from (Dicyclopentadiene, abbreviation DCPD) ring-opening metathetic polymerization it is appropriately crosslinked have both impact and
The thermosetting plastics of high-modulus.It is heat resistance that polydicyclopentadiene engineering plastics have had, creep resistance, dimensional stability, resistance to
The material of the characteristics such as corrosivity, lightweight can be used for manufacturing various premium quality products.Such as: bumper in transportation,
Backplate, side plate, hood and bodyshell etc.；The shell of the large electrics equipment such as motor, air conditioner in electrical equipment；
The component and agricultural machinery of snowmoblie, surfboard, golf cart in sports apparatus etc., civil construction material etc..Beauty
The states such as state, Japan, Europe have been achieved with the industrial production of polydicyclopentadiene, and there are no the poly bis of the domestic trade mark so far in China
Cyclopentadiene production technology and material.
The production of polydicyclopentadiene at present mainly passes through dicyclopentadiene open loop under dual-component catalyst effect and shifts
Polymerization is completed.Dual-component catalyst in air moisture and oxygen it is very sensitive, need to be strict with reaction in use process
It completes in an inert atmosphere, so that the high requirements on the equipment, reaction condition requirement are severe in the production process of polydicyclopentadiene
It carves, increases the production cost of polydicyclopentadiene product.Simultaneously tensile strength of existing product and the tensile properties such as modulus and
Heat resistance is also to be improved.
Summary of the invention
The object of the present invention is to provide a kind of polymerizable composition, polymerizable composition, its composite material and preparation method, the composite material ratios
The tensile strength and modulus of existing cyclic olefin polymer increase, the preparation method be able to solve in the prior art to equipment and
Reaction condition requires stringent problem.
To achieve the goals above, the present invention provides a kind of polymerizable composition, polymerizable composition, and the composition contains cycloolefin, transposition
Polymerization catalyst and glass fibre, relative to the cycloolefin of 100 parts by weight, the content of the glass fibre is 4-40 parts by weight,
The content of the metathesis polymerization catalyst is 0.1-1 parts by weight, wherein the length of the glass fibre is 1.2-15mm.
The present invention also provides the composite materials that any one of the above polymerizable composition, polymerizable composition ring-opening metathesis polymerization obtains.
The present invention also provides the preparation methods of above-mentioned composite material, comprising the following steps: will be described in above-mentioned any one
Polymerizable composition, polymerizable composition is dissolved with solvent, it is made to be uniformly dispersed；Solvent is removed under reduced pressure, obtained fluid composition is injected into pattern
It is interior；Heating carries out ring-opening polymerization.
Through the above technical solutions, in cycloolefin monomers be added length be 1.2-15mm glass fibre can be improved it is poly-
The heat resistance and tensile property of obtained composite material are closed, and composite material can be made under relatively mild conditions, drop
The low production cost of composite material.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of polymerizable composition, polymerizable composition, and the composition contains cycloolefin, metathesis polymerization catalyst and glass fibers
Dimension, relative to the cycloolefin of 100 parts by weight, the content of glass fibre is 4-40 parts by weight, and the content of metathesis polymerization catalyst is
0.1-1 parts by weight.The composition that the glass fibre that above-mentioned length is 1.2-15mm is mixed with cycloolefin is through ring-opening metathesis polymerization
The tensile strength and modulus with higher of obtained composite material.
Wherein, the ring in order to further increase the tensile strength and modulus of cyclopentene composite material, relative to 100 parts by weight
Alkene, the content of glass fibre are 12-25 parts by weight, and the content of metathesis polymerization catalyst is 0.2-0.7 parts by weight.
Composition according to the present invention, above-mentioned cycloolefin is known to those skilled in the art, is that intramolecular has by carbon
With the compound of carbon-to-carbon double bond in the ester ring type structure of atomic building and the ester ring type structure.
Polymerizable composition, polymerizable composition according to the present invention, it is preferable that cycloolefin can be the substitution that carbon atom number is 4-8 or
Unsubstituted cycloolefin, or substituted or unsubstituted norborneol alkenes bicyclic alkene.The list of above-mentioned carbon atom number
Cycloolefin or bicyclic alkene have ring strain preferably, and it is poly- that ring-opening metathesis can occur under the action of metathesis polymerization catalyst
Reaction is closed, polycyclic alkene composite material is obtained.
Wherein, the substituent group as substituted cycloolefin or bicyclic alkene can enumerate the hydrocarbon that carbon atom number is 1-10
Base, halogen atom, the alkyl of carbon atom number 1-10 being substituted with halogen atoms etc..
Specifically, the alkyl as carbon atom number 1-10 can be enumerated: the alkane of the carbon atom numbers such as methyl, ethyl, propyl 1-10
Base；The alkenyl of the carbon atom numbers such as vinyl, acrylic 2-10；The alkynes of the carbon atom numbers 2-10 such as acetenyl, propargyl, 3- butynyl
Base；The aryl of the carbon atom numbers 6-10 such as phenyl, 1- naphthalene, 2- naphthalene；The carbon atom numbers such as cyclopropyl, cyclopenta, cyclohexyl 3-10
Naphthenic base etc..
As halogen atom, fluorine atom, chlorine atom, bromine atom etc. can be enumerated.
As the alkyl for the carbon atom number 1-10 being substituted with halogen atoms, chloromethyl, 2- chloroethyl, fluoroform can be enumerated
Base, pentafluoroethyl group etc..
According to the present invention, in substituted cycloolefin or bicyclic alkene, substituent group can be one or more, preferably feelings
Under condition, substituent group is one.
Polymerizable composition, polymerizable composition according to the present invention, the cycloolefin that carbon atom number is 4-8 can for selected from cyclobutane,
One or more of cyclopentene, cycloheptene and cyclo-octene, norborneol alkenes bicyclic alkene can be for selected from norbornene, bicyclic
One of pentadiene, methyldicyclopentadiene, two rings [2.2.2] oct-2-ene and two rings [2.2.1] hept- 2,5- diene are several
Kind.
Above-mentioned cycloolefin and bicyclic alkene can be used alone, and can also be used in combination of two or more.
Contain metathesis polymerization catalyst in polymerizable composition, polymerizable composition of the invention, to metathesis polymerization catalyst used without spy
It does not limit, can be used those of known.As metathesis polymerization catalyst, can enumerate using transition metal atoms as center atom and knot
Conjunction has transition metal complex made of multiple ions, atom, polyatomic ion and compound etc..The transition metal complex
In, as transition metal atoms, usually using the atom of 5 races, 6 races and 8 races.The atom of each race is not particularly limited, 5 races
Atom can enumerate such as tantalum, and the atom of 6 races can enumerate such as molybdenum and tungsten, and the atom of 8 races can enumerate such as ruthenium and osmium.
Polymerizable composition, polymerizable composition according to the present invention, under preferable case, metathesis polymerization catalyst can be ruthenium carbene compound,
Wherein, ruthenium carbene compound is preferably that two (tricyclohexyl phosphine) benzylidene dichloros close ruthenium, [1,3- bis- (2,4,6- trimethylbenzenes
Base) -2- imidazoline subunit] dichloro (benzylidene) (tricyclohexyl phosphine) conjunction ruthenium, dichloro (adjacent isopropoxy benzene methylene) (three
Cyclohexyl phosphine) (adjacent isopropoxy benzene is sub- for ruthenium (II) and (1,3- bis--(2,4,6- trimethylphenyl) -2- imidazolidine subunit) dichloro
Methyl) close one or more of ruthenium.Ruthenium carbene compound catalytic activity is high, and the ring-opening polymerisation of polymerizable composition, polymerizable composition can be improved
Reactivity, since unreacted cyclenes hydrocarbon content is few so obtained composite material peculiar smell is smaller.Meanwhile ruthenium carbene compound has
Have it is opposite more stable with the moisture in oxygen or air and not easy in inactivation the characteristics of.
Above-mentioned ruthenium carbene compound can for example, by Journal of the American Chemical Society,
1996,118 (1) volume, 100-110 pages or Tetrahedron Letters, 1999,40 (12) volume, 2247-2250 pages
The method of documents record is waited to prepare.It can also be obtained by commercially available mode, such as can be for purchased from Suzhou Xin Nuoke biology section
Skill Co., Ltd, two (tricyclohexyl phosphine) benzylidene dichloros that article number is 44-0001 close ruthenium and article number is 44-0002's
[bis- (2,4,6- the trimethylphenyl) -2- imidazoline subunits of 1,3-] dichloro (benzylidene) (tricyclohexyl phosphine) closes ruthenium.
According to the present invention, glass fibre is added in polymerizable compositions can be improved the drawing for the composite material that polymerization obtains
Intensity and modulus is stretched, the length of glass fibre is not particularly limited, and can be known to the skilled person, preferable case
Under, the length of glass fibre is 1.2-15mm.Enhancing cycloolefin composite wood can be played in the glass fibre of above-mentioned length range
The effect of material, while will not occur agglomeration in forming process.
Polymerizable composition, polymerizable composition according to the present invention, in order to make glass fibre with polymerize after cycloolefin interface interaction
Power enhancing, above-mentioned glass fibre can pass through coupling agent surface treatment, and the type of coupling agent does not require particularly, can be this
It known to the technical staff of field, such as can be one in silane coupling agent, titante coupling agent and aluminium class coupling agent
Kind is several.Under preferable case, glass fibre is surface-treated using silane coupling agent, at silane coupling agent
The fiberglass surfacing smoothness managed reduces, with polymerize after cycloolefin interface between active force enhance, to improve cyclenes
The tensile strength and modulus of hydrocarbon composite material.
Specifically, silane coupling agent can be selected from γ-aminopropyltrimethoxysilane, gamma-aminopropyl-triethoxy silicon
Alkane, vinyltriethoxysilane, vinyltrimethoxysilane, double-(γ-triethoxy silicon substrate propyl) tetrasulfide, γ-
One or more of methacryloxypropyl trimethoxy silane.Wherein, in order to make the processed glass of silane coupling agent
Active force between glass fiber surface and cyclic olefin polymer interface is stronger, under preferable case, selects the idol containing olefin group
Join agent, such as vinyltriethoxysilane, vinyltrimethoxysilane or γ-methacryloxypropyl trimethoxy
Silane.Contain carbon-carbon double bond in the silane coupling agent of mentioned kind, addition reaction can be carried out with the double bond in cycloolefin, at this
In the case of kind, coupling agent one end is connect with glass fibre, and the other end is connect by chemical bond with cycloolefin, effectively enhances glass
Interface interaction power between glass fiber and cyclic olefin polymer, thus improve the tensile strength of composite material that polymerization obtains and
The mechanical properties such as modulus.
Wherein the method for above-mentioned coupling agent treatment glass fibre is not particularly limited, and can be those skilled in the art institute
It is well known, it can be with for example, by using the method for silane coupling agent processing glass fibre are as follows: disperse glass fibre in containing 0.2-
In the dehydrated alcohol of 10% (wt) coupling agent, HCl is added and adjusts pH value to 4-5, ultrasonic disperse reacts 1-2 hours at 50 DEG C.Instead
After answering, glass fibre is taken out, it is extremely neutral wash with distilled water, it dries 2-5 hours, is obtained by silane at 100-120 DEG C
The modified glass fibre in coupling agent surface.
The present invention also provides the composite materials that any one of the above polymerizable composition, polymerizable composition ring-opening metathesis polymerization obtains.Polymerism
The ring-opening polymerisation of composition under preferable case, can be carried out by mass polymerization or solution polymerization process by mass polymerization.
The present invention also provides the preparation methods of above-mentioned composite material, comprising the following steps: uses above-mentioned polymerizable composition, polymerizable composition
A small amount of solvent dissolution, makes it be uniformly dispersed；Solvent is removed under reduced pressure, obtained fluid composition is injected into pattern；Heat up into
Row ring-opening polymerization.
In the preparation method of composite material according to the present invention, dissolution, dispersion and depressurization steps therein are to body
There is no limit as long as guarantee that polymerizable composition, polymerizable composition is uniformly dispersed in a solvent, and system can be smoothly discharged in solvent for the temperature of system
It is outer.Polymerizable composition, polymerizable composition starts reaction before entering shaping mould in order to prevent causes system viscosity to increase, and in dissolution, divides
It dissipates in depressurization steps, the temperature of system is preferably -20 to 30 DEG C, within the scope of the preferred temperature, polymerizable composition, polymerizable composition
Catalyst activity is relatively low, and starting ring-opening polymerization in advance before shaping mould can be entered to avoid polymerizable composition, polymerizable composition causes
System viscosity is got higher, so that composite materials property caused by avoiding the solvent discharge in system insufficient declines.
In the preparation method of composite material according to the present invention, a small amount of solvent can be used and dissolve above-mentioned polymerism
Composition is so that each component is uniformly mixed, and in solution polymerization process, the medium that solvent can be used as polymerization reaction is used.In order to
Avoid the moisture in solvent from inactivating metathesis polymerization catalyst, under preferable case, solvent before use can it is purified processing with
Removing moisture therein etc. influences the impurity of catalyst activity, and the method for above-mentioned purification process is ripe for those skilled in the art
Know, purification process can be carried out to different solvents according to " reagent purification handbook ".
Wherein, it is not required particularly as the type of solvent, as long as meeting solvent is non-live to metathesis polymerization catalyst
Property.Under preferable case, solvent can be for selected from pentane, n-hexane, normal heptane, pentamethylene, hexamethylene, methyl cyclohexane
One of alkane, dimethyl cyclohexane, cyclooctane, benzene,toluene,xylene, Anaesthetie Ether, tetrahydrofuran and methylene chloride are several
Kind.Wherein in order to make solvent be easier discharge system in decompression process, under preferable case, relatively low molten of boiling point is used
Agent, for example, selected from one or more of methylene chloride, Anaesthetie Ether, pentane and tetrahydrofuran.The method of dissolution does not have yet
There is special limitation, as long as guaranteeing that polymerizable composition, polymerizable composition is uniformly mixed, can be added into above-mentioned polymerizable composition, polymerizable composition same
A kind of solvent, agitated or ultrasonic mixing is uniform, can also be by metathesis polymerization catalyst, cycloolefin and glass fibre respectively with few
Its solution is uniformly mixed again after amount solvent dissolution.Above-mentioned mixing and dispersing mode may include stirring, ultrasonic disperse etc..Polymerization
Property mixture dissolution and after mixing, can using solvent therein is discharged by the way of depressurizing, the time of Depressor response with
The pressure of system is not particularly limited, and is emptied the solvent in system as long as meeting, while not causing polymerizable composition, polymerizable composition to mention
Preceding beginning polymerization reaction.
In the preparation method of composite material according to the present invention, answered to reduce in molding composite material
Power, under preferable case, shaping mould can be by preheating, wherein the temperature preheated can be 30- before injecting fluid composition
60℃.The shaping mould of preheated to above-mentioned temperature range can reduce the internal stress of molding composite material, reduce composite material
In crackle and defect, improve the mechanical property of composite material.
In the preparation method of composite material according to the present invention, in order to improve the reaction of cycloolefin ring-opening polymerisation
Rate, heating mode are preferably gradient increased temperature, and specifically, heating sequence can be 40-70 DEG C of the first stage, second stage 100-
130 DEG C, 140-160 DEG C of the phase III, wherein the reaction time in per stage can be 1-4 hours.Using above-mentioned gradient increased temperature side
Formula can make the ring-opening polymerization of cycloolefin more complete, to obtain the better composite material of mechanical property.
The present invention is further illustrated below by embodiment, and still, therefore the present invention should not be any way limited.
Embodiment 1
The present embodiment is for illustrating polymerizable composition, polymerizable composition of the invention.Wherein, glass fibre is purchased from Chongqing world composite wood
Expect that Co., Ltd, dicyclopentadiene and dichloro (adjacent isopropoxy benzene methylene) (tricyclohexyl phosphine) ruthenium (II) are brilliant purchased from Shanghai
Pure reagent Co., Ltd.
Take the dicyclopentadiene of 100 parts by weight, 0.1 parts by weight dichloro (adjacent isopropoxy benzene methylene) (thricyclohexyl
Phosphine) ruthenium (II), the glass fibre that 4 parts by weight length are 15mm is uniformly mixed, obtains the polymerizable composition, polymerizable composition of the present embodiment.
Embodiment 2
The present embodiment is for illustrating polymerizable composition, polymerizable composition of the invention.Wherein, glass fibre is purchased from Chongqing world composite wood
Expect Co., Ltd, norbornene, methyldicyclopentadiene and [1,3- bis- (2,4,6- trimethylphenyl) -2- imidazoline subunits] two
Chlorine (benzylidene) (tricyclohexyl phosphine) closes ruthenium and is purchased from Shanghai crystalline substance pure reagent Co., Ltd.
Take the norbornene of 40 parts by weight, the methyldicyclopentadiene of 60 parts by weight, 1 parts by weight [1,3- bis- (2,4,6- tri-
Aminomethyl phenyl) -2- imidazoline subunit] dichloro (benzylidene) (tricyclohexyl phosphine) conjunction ruthenium, 40 parts by weight length are 1.2-3mm's
Glass fibre is uniformly mixed, and obtains the polymerizable composition, polymerizable composition of the present embodiment.
Embodiment 3
The present embodiment is for illustrating polymerizable composition, polymerizable composition of the invention.Wherein, glass fibre is purchased from Chongqing world composite wood
Expect Co., Ltd, two rings [2.2.1] hept- 2,5- diene, 3- vinyl -1- cyclopentene and two (tricyclohexyl phosphine) benzylidenes two
Chlorine closes ruthenium and is purchased from Shanghai crystalline substance pure reagent Co., Ltd.
Take two rings [2.2.1] hept- 2 of 90 parts by weight, 5- diene, the 3- vinyl -1- cyclopentene of 10 parts by weight, 0.68 weight
It measures part two (tricyclohexyl phosphine) benzylidene dichloro and closes ruthenium, the glass fibre that 12 parts by weight length are 4.5mm is uniformly mixed, obtains
The polymerizable composition, polymerizable composition of the present embodiment.
Embodiment 4
The present embodiment is for illustrating polymerizable composition, polymerizable composition of the invention.Wherein, glass fibre is purchased from Chongqing world composite wood
Expect Co., Ltd, dicyclopentadiene, two rings [2.2.2] oct-2-ene and (1,3- bis--(2,4,6- trimethylphenyl) -2- imidazolidine
Subunit) dichloro (adjacent isopropoxy benzylidene) close ruthenium be purchased from Shanghai crystalline substance pure reagent Co., Ltd.
Take two rings [2.2.2] oct-2-ene of 25 parts by weight, the dicyclopentadiene of 75 parts by weight, 0.2 parts by weight (1,3- bis--
(2,4,6- trimethylphenyl) -2- imidazolidine subunit) dichloro (adjacent isopropoxy benzylidene) closes ruthenium, and 15 parts by weight length are
The glass fibre of 3mm is uniformly mixed, and obtains the polymerizable composition, polymerizable composition of the present embodiment.
Embodiment 5
The present embodiment is for illustrating polymerizable composition, polymerizable composition of the invention.Wherein, glass fibre is purchased from Chongqing world composite wood
Expect Co., Ltd, be surface-treated through vinyltrimethoxysilane, dicyclopentadiene, cycloheptene, 3- vinyl -1- cyclobutane,
Vinyltrimethoxysilane and two (tricyclohexyl phosphine) benzylidene dichloros close ruthenium and are purchased from Shanghai crystalline substance pure reagent Co., Ltd.
Take the dicyclopentadiene of 70 parts by weight, the 3- vinyl -1- cyclobutane of 20 parts by weight, the cycloheptene of 10 parts by weight,
0.43 parts by weight two (tricyclohexyl phosphine) benzylidene dichloro closes ruthenium, and 18 parts by weight length are the glass fibre of 6mm, obtains this reality
Apply the polymerizable composition, polymerizable composition of example.
Embodiment 6
The present embodiment is for illustrating polymerizable composition, polymerizable composition of the invention.Wherein, glass fibre is purchased from Chongqing world composite wood
Expect Co., Ltd, is surface-treated through γ-methacryloxypropyl trimethoxy silane, dicyclopentadiene, cyclo-octene, γ-
Methacryloxypropyl trimethoxy silane and [bis- (2,4,6- the trimethylphenyl) -2- imidazoline subunits of 1,3-] dichloro
(benzylidene) (tricyclohexyl phosphine) closes ruthenium and is purchased from Shanghai crystalline substance pure reagent Co., Ltd.
Take the dicyclopentadiene of 85 parts by weight, the cyclo-octene of 15 parts by weight, 0.32 parts by weight [1,3- bis- (2,4,6- front threes
Base phenyl) -2- imidazoline subunit] dichloro (benzylidene) (tricyclohexyl phosphine) conjunction ruthenium, 25 parts by weight length are the glass of 12mm
Fiber obtains the polymerizable composition, polymerizable composition of the present embodiment.
Embodiment 7
The present embodiment is for illustrating polymerizable composition, polymerizable composition of the invention.
Using polymerizable composition, polymerizable composition same as Example 1, the difference is that glass fibre, through vinyl trimethoxy
Silane surface treatment.
Embodiment 8
The present embodiment is for illustrating polymerizable composition, polymerizable composition of the invention.
Using polymerizable composition same as Example 1, the difference is that dichloro (adjacent isopropoxy benzene methylene)
(tricyclohexyl phosphine) ruthenium (II) is 0.4 parts by weight, and the glass fibre that length is 15mm is 18 parts by weight.
Comparative example 1
This comparative example is used for the polymerizable composition, polymerizable composition for illustrating to be different from the present invention, and the composition does not add glass fibre,
Remaining component and content are same as Example 1.
Embodiment 9
The present embodiment is for illustrating the method that polymerizable composition, polymerizable composition ring-opening polymerisation of the invention prepares composite material.
Polymerizable composition, polymerizable composition in embodiment 1 is placed in 50mL single-necked flask, the pentane of addition 5mL after purification, 30
It is stirred to dissolve at DEG C, vacuumizes the solvent in removing system.Reactant becomes being poured into 30 DEG C of preheatings when thick liquid
Mold in, gradient increased temperature carry out ring-opening polymerization, obtain composite material P1.Warming temperature and time: 70 DEG C of (4h)+130
℃(3h)+160℃(4h)。
Embodiment 10
The present embodiment is for illustrating the method that polymerizable composition, polymerizable composition ring-opening polymerisation of the invention prepares composite material.
Polymerizable composition, polymerizable composition in embodiment 2 is placed in 50mL single-necked flask, the CH of 2mL after purification is added2Cl2, -20
It is stirred to dissolve at DEG C, vacuumizes the solvent in removing system.Reactant becomes being poured into 30 DEG C of preheatings when thick liquid
Mold in gradient increased temperature carry out ring-opening polymerization, obtain composite material P2.Warming temperature and time: 40 DEG C (3h)+100 DEG C
(4h)+150℃(2h)。
Embodiment 11
The present embodiment is for illustrating the method that polymerizable composition, polymerizable composition ring-opening polymerisation of the invention prepares composite material.
Polymerizable composition, polymerizable composition in embodiment 3 is placed in 50mL single-necked flask, the Anaesthetie Ether of addition 5mL after purification, 0
It is stirred to dissolve at DEG C, vacuumizes the solvent in removing system.Reactant becomes being poured into 40 DEG C of preheatings when thick liquid
Mold in, gradient increased temperature carry out ring-opening polymerization, obtain composite material P3.Warming temperature and time: 40 DEG C of (1h)+120
℃(2h)+150℃(2h)。
Embodiment 12
The present embodiment is for illustrating the method that polymerizable composition, polymerizable composition ring-opening polymerisation of the invention prepares composite material.
Polymerizable composition, polymerizable composition in embodiment 4 is placed in 50mL single-necked flask, the tetrahydrofuran of addition 5mL after purification, 0
It is stirred to dissolve at DEG C, vacuumizes the solvent in removing system.Reactant becomes being poured into 60 DEG C of preheatings when thick liquid
Mold in, gradient increased temperature carry out ring-opening polymerization, obtain composite material P4.Warming temperature and time: 60 DEG C of (2h)+125
℃(2h)+150℃(3h)。
Embodiment 13
The present embodiment is for illustrating the method that polymerizable composition, polymerizable composition ring-opening polymerisation of the invention prepares composite material.
It is mono- that dicyclopentadiene, cycloheptene, 3- vinyl -1- cyclobutane and glass fibre in embodiment 5 is placed in 50mL
In mouth flask, the methylene chloride of 2mL after purification is added, is stirred to dissolve at 0 DEG C, the metathesis polymerization in embodiment 5 is catalyzed
Agent two (tricyclohexyl phosphine) benzylidene dichloro closes ruthenium and is placed in another 50mL single-necked flask, and the dichloro of 1mL after purification is added
Methane is stirred to dissolve at 0 DEG C, after two parts solution is mixed evenly at 0 DEG C, is vacuumized molten in removing system
Agent.Reactant becomes being poured into when thick liquid in the mold of 50 DEG C of preheatings, and gradient increased temperature carries out ring-opening polymerization, obtains
Composite material P5.Warming temperature and time: 60 DEG C (2h)+150 DEG C of+120 DEG C (2h) (3h).
Embodiment 14
The present embodiment is for illustrating the method that polymerizable composition, polymerizable composition ring-opening polymerisation of the invention prepares composite material.
Dicyclopentadiene, cyclo-octene and glass fibre in embodiment 6 is placed in 50mL single-necked flask, it is pure that 2mL is added
Methylene chloride after change stirs to dissolve at 0 DEG C, by the metathesis polymerization catalyst [1,3- bis- (2,4,6- tri- in embodiment 6
Aminomethyl phenyl) -2- imidazoline subunit] dichloro (benzylidene) (tricyclohexyl phosphine) close ruthenium be placed in another 50mL single-necked flask
In, the methylene chloride of 1mL after purification is added, is stirred to dissolve at 0 DEG C, two parts solution is mixed evenly at 0 DEG C
Afterwards, the solvent in removing system is vacuumized.Reactant becomes being poured into when thick liquid in the mold of 45 DEG C of preheatings, gradient liter
Temperature carries out ring-opening polymerization, obtains composite material P6.Warming temperature and time: 60 DEG C (2h)+125 DEG C (3h)+160 DEG C
(2h)。
Embodiment 15
The present embodiment is for illustrating the method that polymerizable composition, polymerizable composition ring-opening polymerisation of the invention prepares composite material.
Composite material P7 is prepared using method same as Example 9 in polymerizable composition in embodiment 7.
Embodiment 16
The present embodiment is for illustrating the method that polymerizable composition, polymerizable composition ring-opening polymerisation of the invention prepares composite material.
Composite material P8 is prepared using method same as Example 9 in polymerizable composition in embodiment 8.
Comparative example 2
The preparation method for the cycloolefin composite material that this comparative example is used to illustrate to be different from the present invention.Using with embodiment 9
Cyclic olefin polymer D1 is prepared through ring-opening polymerization in polymerizable composition, polymerizable composition in comparative example 1 by identical method.
Comparative example 3
The preparation method for the cycloolefin composite material that this comparative example is used to illustrate to be different from the present invention.Using with embodiment 9
Identical polymerizable composition, polymerizable composition and preparation method, except that solvent is removed without decompression, ring-opening polymerisation temperature is 150 DEG C,
Reaction 8 hours, is prepared cyclic olefin polymer D2.
Testing example 1
Composite material P1-P6 and D1-D2 that above-described embodiment 9-16 and comparative example 2-3 are prepared are subjected to dynamic respectively
Mechanical analysis (DMA) and tensile property test, test obtain Tg, stretch modulus and tensile break strength data are listed in Table 1 below.
Wherein, the tensile property of sample is tested by U.S. INSTRON-5567 type universal testing machine.Reference
GB/T 2567-2008 standard.Every group of test at least five sample, test rate 2mm/min.
The dynamic mechanical analysis (DMA) of sample is surveyed using the Q800 type dynamic thermomechanical analysis apparatus of U.S. TA company
Examination.Using single-cantilever mode, sample is having a size of 40 × 7 × 2mm3.Heating rate is 3 DEG C/min, and temperature elevating range is 25-220 DEG C,
Loading frequency is 1Hz.
Table 1
| Material | Tg/℃ | Tensile break strength/MPa | Stretch modulus/MPa | |
| Embodiment 9 | P1 | 124.9 | 51.4 | 2885 |
| Embodiment 10 | P2 | 139.6 | 62.7 | 3897 |
| Embodiment 11 | P3 | 129.1 | 52.8 | 3204 |
| Embodiment 12 | P4 | 131.2 | 54.9 | 3242 |
| Embodiment 13 | P5 | 133.4 | 57.3 | 3397 |
| Embodiment 14 | P6 | 137.2 | 58.2 | 3652 |
| Embodiment 15 | P7 | 134.5 | 56.4 | 3502 |
| Embodiment 16 | P8 | 136.7 | 59.8 | 3415 |
| Comparative example 2 | D1 | 122.5 | 49.1 | 2453 |
| Comparative example 3 | D2 | 124.7 | 51.0 | 2872 |
It can be seen that from the data in table 1 relative to the cyclic olefin polymer D1 for not adding glass fibre, of the invention answers
The glass fibre that length is 1.2-15mm is added in condensation material P1-P8 in cycloolefin, so that the glass transition temperature of composite material
Spend TgAnd tensile break strength and stretch modulus are all improved, and illustrate that the heat resistance of composite material and tensile property are changed
It is kind.And it can be seen that from the data comparison of P7-8 and P1 in the currently preferred cycloolefin relative to 100 parts by weight, glass
The content of fiber is 12-25 parts by weight, and the content of metathesis polymerization catalyst is 0.2-0.7 parts by weight, and glass fibre is by even
In the case that connection agent is surface-treated, the heat resistance and tensile property of obtained composite material are more prominent.On the other hand, from
The data comparison of composite material P1 and D2 can be seen that removes solvent using first dissolution polymerizable composition, polymerizable composition of the invention again, and
There is better heat resistance and tensile property using the composite material that the method that gradient increased temperature is allowed to ring-opening polymerisation is prepared, together
When, the preparation method reaction condition is mild, simple and easy to operate.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (9)
1. a kind of polymerizable composition, polymerizable composition, it is characterised in that: the composition contains cycloolefin, metathesis polymerization catalyst and glass fibers
Dimension, relative to the cycloolefin of 100 parts by weight, the content of the glass fibre is 12-25 parts by weight, the metathesis polymerization catalyst
Content be 0.2-0.7 parts by weight, wherein the length of the glass fibre is 1.2-15mm, and the metathesis polymerization catalyst is
Ruthenium carbene compound, the ruthenium carbene compound be closed selected from two (tricyclohexyl phosphine) benzylidene dichloros ruthenium, [it is 1,3- bis- (2,
4,6- trimethylphenyl) -2- imidazoline subunit] dichloro (benzylidene) (tricyclohexyl phosphine) conjunction ruthenium, dichloro (adjacent isopropoxy benzene
Methylene) (tricyclohexyl phosphine) ruthenium (II) and (1,3- bis--(2,4,6- trimethylphenyl) -2- imidazolidine subunit) dichloro it is (adjacent
Isopropoxy benzylidene) close one or more of ruthenium.
2. polymerizable composition, polymerizable composition according to claim 1, it is characterised in that: the cycloolefin is that carbon atom number is 4-8's
Substituted or unsubstituted cycloolefin or the substituted or unsubstituted bicyclic alkene of norborneol alkenes.
3. polymerizable composition, polymerizable composition according to claim 2, it is characterised in that: the carbon atom number is the cycloolefin of 4-8
For selected from one or more of cyclobutane, cyclopentene, cycloheptene and cyclo-octene, the norborneol alkenes bicyclic alkene be selected from
Norbornene, dicyclopentadiene, methyldicyclopentadiene, two rings [2.2.2] oct-2-ene and two rings [2.2.1] hept- 2,5- diene
One or more of.
4. polymerizable composition, polymerizable composition according to claim 1, it is characterised in that: the glass fibre is by coupling agent surface
Reason, wherein the coupling agent is selected from one of silane coupling agent, titante coupling agent and aluminium class coupling agent or several
Kind.
5. the composite material that polymerizable composition, polymerizable composition ring-opening metathesis polymerization described in any one of claim 1-4 obtains.
6. the preparation method of composite material described in claim 5, it is characterised in that: the following steps are included: by claim 1-5
Any one of described in polymerizable composition, polymerizable composition dissolved with solvent, so that it is uniformly dispersed；Solvent is removed under reduced pressure, the liquid that will be obtained
Composition is injected into pattern；Heating carries out ring-opening polymerization.
7. the preparation method of composite material according to claim 6, it is characterised in that: the dissolution, dispersion and blowdown step
In rapid, temperature is -20 to 30 DEG C, and the solvent can be for selected from pentane, n-hexane, normal heptane, pentamethylene, hexamethylene, first
One in butylcyclohexane, dimethyl cyclohexane, cyclooctane, benzene,toluene,xylene, Anaesthetie Ether, tetrahydrofuran and methylene chloride
Kind is several.
8. the preparation method of composite material according to claim 6, it is characterised in that: the shaping mould is by preheating, in advance
Hot temperature is 30-60 DEG C.
9. the preparation method of composite material according to claim 6, it is characterised in that: the heating is gradient increased temperature, is risen
Docile sequence is 40-70 DEG C of the first stage, 100-130 DEG C of second stage, 140-160 DEG C of the phase III, wherein the reaction in per stage
Time is 1-4 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510981717.3A CN106905482B (en) | 2015-12-23 | 2015-12-23 | A kind of polymerizable composition, polymerizable composition and its composite material and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510981717.3A CN106905482B (en) | 2015-12-23 | 2015-12-23 | A kind of polymerizable composition, polymerizable composition and its composite material and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106905482A CN106905482A (en) | 2017-06-30 |
| CN106905482B true CN106905482B (en) | 2019-09-17 |
Family
ID=59206059
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510981717.3A Active CN106905482B (en) | 2015-12-23 | 2015-12-23 | A kind of polymerizable composition, polymerizable composition and its composite material and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106905482B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827318A (en) * | 2011-12-30 | 2012-12-19 | 洛阳智颢工程塑料有限公司 | Polydicyclopentadiene building template material and its preparation method |
| CN103665700A (en) * | 2013-08-27 | 2014-03-26 | 河南科技大学 | Polydicyclopentadiene composite material and preparation method thereof |
| CN104448084A (en) * | 2014-11-29 | 2015-03-25 | 安徽丹凤集团桐城玻璃纤维有限公司 | Preparation process of glass fiber composite material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1614410B1 (en) * | 2004-06-30 | 2011-08-10 | Ivoclar Vivadent AG | Dental materials polymerizable by photo-induced ring-opening metathesis polymerization of cyclic olefins |
-
2015
- 2015-12-23 CN CN201510981717.3A patent/CN106905482B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102827318A (en) * | 2011-12-30 | 2012-12-19 | 洛阳智颢工程塑料有限公司 | Polydicyclopentadiene building template material and its preparation method |
| CN103665700A (en) * | 2013-08-27 | 2014-03-26 | 河南科技大学 | Polydicyclopentadiene composite material and preparation method thereof |
| CN104448084A (en) * | 2014-11-29 | 2015-03-25 | 安徽丹凤集团桐城玻璃纤维有限公司 | Preparation process of glass fiber composite material |
Non-Patent Citations (1)
| Title |
|---|
| 聚双环戊二烯的合成及其改性研究;任翔;《中国优秀硕士学位论文工程科技I辑》;20150715(第7期);B016-189 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106905482A (en) | 2017-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1204151C (en) | Polymerization of low grade PCPD monomers using an olefin metathesis catalyst | |
| KR102324393B1 (en) | Composition for cured resin and cured product thereof | |
| KR101542338B1 (en) | Epoxy resin composition and fiber-reinforced composite material | |
| JP6475729B2 (en) | Functionalized resins for high performance tires | |
| CN102286139B (en) | Toughened epoxy resin composition containing dicyclopentadiene ester ring structure | |
| JPWO2015046028A1 (en) | Norbornene-based crosslinked polymer and process for producing the same | |
| CN107022044A (en) | A kind of modified dicyclopentadiene material and preparation method thereof | |
| JP2013124341A (en) | Polymer, molded article and method for producing the polymer | |
| WO2016152623A1 (en) | Resin molded body and method for producing same | |
| CN1289551C (en) | Method for preparing low cis-polybutadiene by stepwise excitation | |
| CN105670194B (en) | A kind of IPN high molecule alloy materials of polydicyclopentadiene/macromolecular elastomer and preparation method thereof | |
| CN106905482B (en) | A kind of polymerizable composition, polymerizable composition and its composite material and preparation method | |
| JP2010116458A (en) | Ring-opened copolymer, method for manufacturing the same, and polymer composition | |
| US8604143B2 (en) | Catalysts for polymerization of isoprene and preparations and uses thereof | |
| CN105482373B (en) | A kind of method of epoxy terminated polystyrene oligomer Toughening Modification of Epoxy | |
| JPWO2016158677A1 (en) | Cycloolefin ring-opening copolymer and process for producing the same | |
| CN106905483A (en) | A kind of cyclic olefine copolymer and preparation method thereof | |
| EP3141303B1 (en) | Grubbs-hoveyda type catalyst for metathesis reactions in highly reactive environments | |
| KR102041531B1 (en) | A method for controlling hardening rate of polydicyclopentadiene | |
| CN117069945B (en) | Organic silicon resin toughening agent, single-component high-strength epoxy structural adhesive and preparation method thereof | |
| JP4232350B2 (en) | Norbornene resin and method for producing molded product | |
| Samejima et al. | Formation and properties of elastomer-modified epoxy resins | |
| JPS6392625A (en) | Crosslinked polymer molding, its production and combination of reactive solutions | |
| JP2002363264A (en) | Method for producing norbornene resin | |
| CN106589195B (en) | A method of preparing polyisoprene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230309 Address after: 215513 No.9, research institute road, Changshu Economic and Technological Development Zone, Suzhou City, Jiangsu Province Patentee after: SUZHOU GALAXY ELECTRONIC TECHNOLOGY Co.,Ltd. Address before: 215500 No.9, research institute road, Changshu Economic and Technological Development Zone, Suzhou City, Jiangsu Province Patentee before: CHANGSHU RESEARCH INSTITUTE OF DLUT Co.,Ltd. |