CN107022044A - A kind of modified dicyclopentadiene material and preparation method thereof - Google Patents
A kind of modified dicyclopentadiene material and preparation method thereof Download PDFInfo
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- 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
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Abstract
The present invention relates to a kind of modified dicyclopentadiene material and preparation method thereof, described modification dicyclopentadiene material is using dicyclopentadiene monomer, catalyst and inorganic enhancing component as raw material, it is prepared from by reaction and injection molding process, wherein, the mass ratio of described dicyclopentadiene monomer and catalyst is 100 800:1, the addition of described inorganic enhancing component is the 0.1 1% of dicyclopentadiene monomer mass.Compared with prior art, preparation technology of the present invention is simple, can be effectively dispersed by inorganic enhancing component and the progress of dicyclopentadiene monomer, can be prevented effectively from agglomeration, under ring-opening metathesis polymerization effect, inorganic enhancing component forms full interpenetrating net polymer with polydicyclopentadiene, reaches and polydicyclopentadiene activeness and quietness is acted on, and reaction shaping speed is fast, production efficiency is high, it is easy to carry out Automated condtrol, is adapted to large-scale industrial production, with good application prospect.
Description
Technical field
The invention belongs to polymer material molding processing technique field, be related to a kind of modified dicyclopentadiene material and its
Preparation method.
Background technology
Polydicyclopentadiene (PDCPD) is that a kind of thermosetting prepared by dicyclopentadiene loop-opening polymerisation is moulded
Material, generally using injection moulding (RIM：Reaction Injection Moulding) technique sintetics, it is mainly used in vapour
In terms of turner industry, electrical equipment, working entertainment, building.Reaction and injection molding process (RIM) is by two or more liquid
State monomer or prepolymer are added separately in blender with certain proportion, and pressurization is lower well mixed, is expelled to immediately in Guan Bi mould,
Finally polymeric articles are solidify to form in in-site polymerization.Therefore, the technique have that shaping is fast, the cycle is short, consume energy less, product matter
Measured advantage.
RIM techniques are 1970s Later developments, are used primarily in polyurethane material, but applied to poly-
Started to walk in dicyclopentadiene polymerization studies relatively later, be primarily due to be used for RIM techniques to DCPD monomer purities requirement height.
1985, Hercules companies of the U.S. successfully developed the poly bis ring penta of new RIM resins by raw material of dicyclopentadiene
Diene, PDCPD-RIM is just developed.The polydicyclopentadiene of PDCPD-RIM technique productions has excellent mechanical property, phase
The impact strength and bending modulus answered are higher than PA-RIM and PU-RIM, mainstream product such as U.S. He Gelisi companies and Japan
The solid strange company of trie of METTON, U.S. BF that Di Ren companies develop jointly and the PENTAM that Nippon Zeon Co., Ltd. develops jointly.
The characteristic of inorganic material in itself has directiveness for carrying out composite modification, being capable of lacking for polymeric material
The modification of row target is trapped into, so that Material cladding, which is modified, has designability.Inorganic material is such as：Nano imvite, Nano carbon fibers
Dimension, nano aluminium oxide etc., can strengthen the performance such as high temperature resistant, anticorrosive, high-modulus so that inorganic compounding is material modified wide
It is general to be applied to the fields such as automobile industry, building industry, medical science.Because inorganic material and dicyclopentadiene are in reaction injection molding mistake
Cheng Zhong, inorganic material can form good interface cohesion with dicyclopentadiene material, can give full play to the poly bis ring of enhancing
The high-strength and high-modulus characteristic of pentadiene, improves the mechanical performance of composite modification material.
At present, the report on modified dicyclopentadiene material is relatively fewer.Application No. 201410174826.X's
Chinese invention patent discloses a kind of macromolecular polymeric phenol and is modified dicyclopentadiene material and preparation method thereof, and the modification is poly bis
Cyclopentadiene material is, using dicyclopentadiene monomer, major catalyst, co-catalyst and macromolecular polymeric phenol as raw material, to pass through reaction
What injection molding technique was made；Wherein, the mol ratio of the dicyclopentadiene monomer, major catalyst, co-catalyst for 1000~
2000:1:15~30, the addition of the macromolecular polymeric phenol is the 1%~10% of dicyclopentadiene monomer mass.However, on
The catalyst system that patent is used is stated, it is sensitive to water, oxygen, it need to carry out under nitrogen protection, so as to make it have limitation.
The content of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind can the group of being prevented effectively from
Poly- phenomenon, reaction shaping speed is fast, and production efficiency is high, is remarkably improved the modification polydicyclopentadiene material of the strength of materials and toughness
Material.
Another object of the present invention is just to provide the preparation method of above-mentioned modified dicyclopentadiene material.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of modified dicyclopentadiene material, the material is with dicyclopentadiene monomer, catalyst and inorganic enhancing
Component is raw material, is prepared from by reaction and injection molding process, wherein, described dicyclopentadiene monomer and the matter of catalyst
Amount is than being 100-800:1, the addition of described inorganic enhancing component is the 0.1-1% of dicyclopentadiene monomer mass.
Described dicyclopentadiene monomer is polymer grade dicyclopentadiene monomer.
Described catalyst includes one kind in bicomponent catalyst or single component catalyst.
Described bicomponent catalyst be using the compound or complex compound of transition metal as the first catalyst component, with
Louis's highly basic is used as the second catalyst component.
Described transition metal includes one kind in Ti, Ni, Mo or Ru.
Described single-component catalyst is the monomolecular catalytic agent containing metal carbene.
In the structure of described metal carbene, metallic atom is transition metal atom.
Described inorganic enhancing component includes one kind in nano imvite, kaolin, iron content kaolin or glass fibre
Or it is several.
A kind of preparation method of modified dicyclopentadiene material, this method specifically includes following steps：
Step (1)：Inorganic enhancing component and dicyclopentadiene monomer are carried out into blending to disperse, it is ultrasonically treated, make inorganic increasing
Strong component is completely homogeneously dispersed in dicyclopentadiene monomer, and blend is made；
Step (2)：Obtained blend and catalyst are added sequentially in reaction injection molding reactor, are well mixed
Afterwards, in injection mould, polymerizing curable shaping is carried out, that is, described modification dicyclopentadiene material is made.
The ultrasonically treated time is 0.5-3 hours in step (1), and ultrasonically treated temperature is 25~60 DEG C, and supersonic frequency is
35KHz or 53KHz, ultrasonic power is 100~250W.
The temperature that polymerizing curable is molded in step (2) is 25-50 DEG C, and injection speed is 10-150mL per second, injection pressure
For 0.1~1.2MPa.
In the present invention, the catalyst used both can be catalyst solid powder, or with dichloromethane, acetic acid
The catalyst solution that ethyl ester, tetrahydrofuran, pyridine etc. are formed.Transition metal in catalyst is preferably Ru.Catalyst
Using preceding need using a small amount of solvent carry out ultrasonic dissolution, solvent for use is mainly tetrahydrofuran, pyridine, ethyl acetate etc..
The mentality of designing of the present invention is under the premise of the stable high catalytic activity for keeping catalyst to have, pointedly to add
Enter inorganic enhancing component to strengthen defect performance, end reaction injection moulding obtains being modified dicyclopentadiene material, real
Now it is modified steadily improving for dicyclopentadiene material mechanical property.In actual fabrication process, inorganic enhancing component is equably
It is scattered in dicyclopentadiene monomer, the generation of agglomeration can be prevented effectively from, it is inorganic to increase under ring-opening metathesis polymerization effect
Strong component forms full interpenetrating net polymer with polydicyclopentadiene, reaches and polydicyclopentadiene activeness and quietness is acted on.
Compared with prior art, the invention has the characteristics that：
1) used herein low to inorganic material wide material sources, cost, the pretreatment to inorganic enhancing component is simple, very
Directly used to not handling, the polydicyclopentadiene technological process of production need not be changed, and directly be used, and be easy to factory to promote
Using；
2) present invention can be effectively dispersed by inorganic enhancing component and the progress of dicyclopentadiene monomer, can effectively keep away
Exempt from inorganic enhancing component fine dispersion in matrix material after agglomeration, reaction injection molding；
3) synthetic method of modification dicyclopentadiene material of the invention, using injection reaction moulding process, suffered ring
Border factor is few, reaction shaping speed is fast, production efficiency is high, technique is simple and convenient to operate, is easy to carry out Automated condtrol, is adapted to
Large-scale industrial production；
4) using the present invention synthesized by modification dicyclopentadiene material there are wide market prospects, automobile industry,
The fields such as building industry, medical science are with a wide range of applications.
Embodiment
With reference to specific embodiment, the present invention is described in detail.
Embodiment 1
Dicyclopentadiene material in the present embodiment, using dicyclopentadiene monomer, Grubbs ruthenium catalysts as raw material, is adopted
It is prepared from reaction and injection molding process.Dicyclopentadiene monomer is polymer grade；Catalyst is Grubbs catalyst acetic acid second
Ester solution；The mass ratio of dicyclopentadiene monomer and Grubbs ruthenium catalysts is 600:1；Injection molding reaction temperature is 30
℃。
The preparation method of the dicyclopentadiene material of the present embodiment, comprises the following steps：
Ethyl acetate is used for solvent, Grubbs ruthenium catalysts progress ultrasonic dissolution is disperseed, Grubbs catalysis is obtained
Agent ethyl acetate solution；Grubbs catalyst acetic acid ethyl ester solution and the dicyclopentadiene feedstock being refining to obtain are carried out uniformly altogether
In-mold molding that is mixed, injecting immediately under 30 DEG C of insulations, both obtains dicyclopentadiene material.Last batten processing, carries out mechanics
Performance test, test result is shown in Table 1.
Embodiment 2
Dicyclopentadiene material in the present embodiment, using dicyclopentadiene monomer, Grubbs ruthenium catalysts as raw material, is adopted
It is prepared from reaction and injection molding process.Dicyclopentadiene monomer is polymer grade；Catalyst is Grubbs catalyst acetic acid second
Ester solution；The mass ratio of dicyclopentadiene monomer and Grubbs ruthenium catalysts is 600:1；Injection molding reaction temperature is 35
℃。
The preparation method of the dicyclopentadiene material of the present embodiment, comprises the following steps：
Ethyl acetate is used for solvent, Grubbs ruthenium catalysts progress ultrasonic dissolution is disperseed, Grubbs catalysis is obtained
Agent ethyl acetate solution；Grubbs catalyst acetic acid ethyl ester solution and the dicyclopentadiene feedstock being refining to obtain are carried out uniformly altogether
In-mold molding that is mixed, injecting immediately under 35 DEG C of insulations, both obtains dicyclopentadiene material.Last batten processing, carries out mechanics
Performance test, test result is shown in Table 1.
Embodiment 3
Dicyclopentadiene material in the present embodiment, using dicyclopentadiene monomer, Grubbs ruthenium catalysts as raw material, is adopted
It is prepared from reaction and injection molding process.Dicyclopentadiene monomer is polymer grade；Catalyst is Grubbs catalyst acetic acid second
Ester solution；The mass ratio of dicyclopentadiene monomer and Grubbs ruthenium catalysts is 600:1；Injection molding reaction temperature is 40
℃。
The preparation method of the dicyclopentadiene material of the present embodiment, comprises the following steps：
Ethyl acetate is used for solvent, Grubbs ruthenium catalysts progress ultrasonic dissolution is disperseed, Grubbs catalysis is obtained
Agent ethyl acetate solution；Grubbs catalyst acetic acid ethyl ester solution and the dicyclopentadiene feedstock being refining to obtain are carried out uniformly altogether
In-mold molding that is mixed, injecting immediately under 40 DEG C of insulations, both obtains dicyclopentadiene material.Last batten processing, carries out mechanics
Performance test, test result is shown in Table 1.
Embodiment 4
Dicyclopentadiene material in the present embodiment, using dicyclopentadiene monomer, Grubbs ruthenium catalysts as raw material, is adopted
It is prepared from reaction and injection molding process.Dicyclopentadiene monomer is polymer grade；Catalyst is Grubbs catalyst acetic acid second
Ester solution；The mass ratio of dicyclopentadiene monomer and Grubbs ruthenium catalysts is 600:1；Injection molding reaction temperature is 45
℃。
The preparation method of the dicyclopentadiene material of the present embodiment, comprises the following steps：
Ethyl acetate is used for solvent, Grubbs ruthenium catalysts progress ultrasonic dissolution is disperseed, Grubbs catalysis is obtained
Agent ethyl acetate solution；Grubbs catalyst acetic acid ethyl ester solution and the dicyclopentadiene feedstock being refining to obtain are carried out uniformly altogether
In-mold molding that is mixed, injecting immediately under 45 DEG C of insulations, both obtains dicyclopentadiene material.Last batten processing, carries out mechanics
Performance test, test result is shown in Table 1.
Influence of the reaction injection molding temperature of table 1 to dicyclopentadiene material performance
| Embodiment | Forming temperature (DEG C) | Tensile strength/MPa | Stretch modulus/MPa | Impact strength/MPa |
| Embodiment 1 | 30 | 47 | 2094 | 14 |
| Embodiment 2 | 35 | 54 | 2110 | 18 |
| Embodiment 3 | 40 | 53 | 2121 | 18 |
| Embodiment 4 | 45 | 50 | 2100 | 16 |
Note：The mass ratio of dicyclopentadiene monomer and Grubbs ruthenium catalysts is 600:1.
Embodiment 5
Dicyclopentadiene material in the present embodiment, using dicyclopentadiene monomer, Grubbs ruthenium catalysts as raw material, is adopted
It is prepared from reaction and injection molding process.Dicyclopentadiene monomer is polymer grade；Catalyst is Grubbs catalyst acetic acid second
Ester solution；The mass ratio of dicyclopentadiene monomer and Grubbs ruthenium catalysts is 600:1；Injection molding reaction temperature is 35
℃.The kaolinic addition is the 0.1% of dicyclopentadiene monomer mass, and described injecting forming temperature is 35 DEG C.
The preparation method of the modification dicyclopentadiene material of the present embodiment, comprises the following steps：
Ethyl acetate is used for solvent, Grubbs ruthenium catalysts progress ultrasonic dissolution is disperseed, Grubbs rutheniums system is formed
Catalyst acetic acid ethyl ester solution；Meanwhile, it is scattered that kaolin carries out ultrasound 2h blendings with dicyclopentadiene.Grubbs ruthenium catalysts
Ethyl acetate solution and dicyclopentadiene kaolin solution are dispersed, the in-mold molding injected immediately under 35 DEG C of insulations, both
Obtain Modification of kaolin dicyclopentadiene material.Last batten processing, carries out Mechanics Performance Testing, test result is shown in Table 2.
Embodiment 6
Dicyclopentadiene material in the present embodiment, using dicyclopentadiene monomer, Grubbs ruthenium catalysts as raw material, is adopted
It is prepared from reaction and injection molding process.Dicyclopentadiene monomer is polymer grade；Catalyst is Grubbs catalyst acetic acid second
Ester solution；The mass ratio of dicyclopentadiene monomer and Grubbs ruthenium catalysts is 600:1；Injection molding reaction temperature is 35
℃.The kaolinic addition is the 0.3% of dicyclopentadiene monomer mass, and described injecting forming temperature is 35 DEG C.
The preparation method of the modification dicyclopentadiene material of the present embodiment, comprises the following steps：
Ethyl acetate is used for solvent, Grubbs ruthenium catalysts progress ultrasonic dissolution is disperseed, Grubbs rutheniums system is formed
Catalyst acetic acid ethyl ester solution；Meanwhile, it is scattered that kaolin carries out ultrasound 2h blendings with dicyclopentadiene.Grubbs ruthenium catalysts
Ethyl acetate solution and dicyclopentadiene kaolin solution are dispersed, the in-mold molding injected immediately under 35 DEG C of insulations, both
Obtain Modification of kaolin dicyclopentadiene material.Last batten processing, carries out Mechanics Performance Testing, test result is shown in Table 2.
Embodiment 7
Dicyclopentadiene material in the present embodiment, using dicyclopentadiene monomer, Grubbs ruthenium catalysts as raw material, is adopted
It is prepared from reaction and injection molding process.Dicyclopentadiene monomer is polymer grade；Catalyst is Grubbs catalyst acetic acid second
Ester solution；The mass ratio of dicyclopentadiene monomer and Grubbs ruthenium catalysts is 600:1；Injection molding reaction temperature is 35
℃.The kaolinic addition is the 0.6% of dicyclopentadiene monomer mass, and described injecting forming temperature is 35 DEG C.
The preparation method of the modification dicyclopentadiene material of the present embodiment, comprises the following steps：
Ethyl acetate is used for solvent, Grubbs ruthenium catalysts progress ultrasonic dissolution is disperseed, Grubbs rutheniums system is formed
Catalyst acetic acid ethyl ester solution；Meanwhile, it is scattered that kaolin carries out ultrasound 2h blendings with dicyclopentadiene.Grubbs ruthenium catalysts
Ethyl acetate solution and dicyclopentadiene kaolin solution are dispersed, the in-mold molding injected immediately under 35 DEG C of insulations, both
Obtain Modification of kaolin dicyclopentadiene material.Last batten processing, carries out Mechanics Performance Testing, test result is shown in Table 2.
Embodiment 8
Dicyclopentadiene material in the present embodiment, using dicyclopentadiene monomer, Grubbs ruthenium catalysts as raw material, is adopted
It is prepared from reaction and injection molding process.Dicyclopentadiene monomer is polymer grade；Catalyst is Grubbs catalyst acetic acid second
Ester solution；The mass ratio of dicyclopentadiene monomer and Grubbs ruthenium catalysts is 600:1；Injection molding reaction temperature is 35
℃.The kaolinic addition is the 0.9% of dicyclopentadiene monomer mass, and described injecting forming temperature is 35 DEG C.
The preparation method of the modification dicyclopentadiene material of the present embodiment, comprises the following steps：
Ethyl acetate is used for solvent, Grubbs ruthenium catalysts progress ultrasonic dissolution is disperseed, Grubbs rutheniums system is formed
Catalyst acetic acid ethyl ester solution；Meanwhile, it is scattered that kaolin carries out ultrasound 2h blendings with dicyclopentadiene.Grubbs ruthenium catalysts
Ethyl acetate solution and dicyclopentadiene kaolin solution are dispersed, the in-mold molding injected immediately under 35 DEG C of insulations, both
Obtain Modification of kaolin dicyclopentadiene material.Last batten processing, carries out Mechanics Performance Testing, test result is shown in Table 2.
Influence of the kaolin addition of table 2 to dicyclopentadiene material performance
| Embodiment | Kaolin/% | Tensile strength/MPa | Stretch modulus/MPa | Impact strength/MPa |
| Embodiment 2 | 0 | 54 | 2110 | 18 |
| Embodiment 5 | 0.1 | 56 | 2117 | 10 |
| Embodiment 6 | 0.3 | 58 | 2115 | 13 |
| Embodiment 7 | 0.6 | 52 | 2089 | 13 |
| Embodiment 8 | 0.9 | 50 | 2006 | 10 |
Note：The mass ratio of dicyclopentadiene monomer and Grubbs ruthenium catalysts is 600:1；Forming temperature is 35 DEG C.
Embodiment 9
Dicyclopentadiene material in the present embodiment, using dicyclopentadiene monomer, Grubbs ruthenium catalysts as raw material, is adopted
It is prepared from reaction and injection molding process.Dicyclopentadiene monomer is polymer grade；Catalyst is Grubbs catalyst acetic acid second
Ester solution；The mass ratio of dicyclopentadiene monomer and Grubbs ruthenium catalysts is 600:1；Injection molding reaction temperature is 35
℃.The kaolinic addition of iron content is the 0.3% of dicyclopentadiene monomer mass, and described injecting forming temperature is 35
℃。
The preparation method of the modification dicyclopentadiene material of the present embodiment, comprises the following steps：
Ethyl acetate is used for solvent, Grubbs ruthenium catalysts progress ultrasonic dissolution is disperseed, Grubbs rutheniums system is formed
Catalyst acetic acid ethyl ester solution；Meanwhile, it is scattered that iron content kaolin carries out ultrasound 2h blendings with dicyclopentadiene.Grubbs rutheniums system urges
Agent ethyl acetate solution and dicyclopentadiene iron content kaolin solution are dispersed, inject immediately in the mould under 35 DEG C of insulations
Shaping, both obtains iron content Modification of kaolin dicyclopentadiene material.Last batten processing, carries out Mechanics Performance Testing, test knot
Fruit is shown in Table 3.
Embodiment 10
Dicyclopentadiene material in the present embodiment, using dicyclopentadiene monomer, Grubbs ruthenium catalysts as raw material, is adopted
It is prepared from reaction and injection molding process.Dicyclopentadiene monomer is polymer grade；Catalyst is Grubbs catalyst acetic acid second
Ester solution；The mass ratio of dicyclopentadiene monomer and Grubbs ruthenium catalysts is 600:1；Injection molding reaction temperature is 35
℃.The addition of the glass fibre is the 0.3% of dicyclopentadiene monomer mass, and described injecting forming temperature is 35 DEG C.
The preparation method of the modification dicyclopentadiene material of the present embodiment, comprises the following steps：
Ethyl acetate is used for solvent, Grubbs ruthenium catalysts progress ultrasonic dissolution is disperseed, Grubbs rutheniums system is formed
Catalyst acetic acid ethyl ester solution；Meanwhile, it is scattered that glass fibre carries out ultrasound 2h blendings with dicyclopentadiene.Grubbs rutheniums system is catalyzed
Agent ethyl acetate solution and dicyclopentadiene mixture of glass fibers are dispersed, inject immediately 35 DEG C of lower moulds of insulation it is interior into
Type, had both obtained glass fibre and has been modified dicyclopentadiene material.Last batten processing, carries out Mechanics Performance Testing, test result is shown in
Table 3.
Embodiment 11
Dicyclopentadiene material in the present embodiment, using dicyclopentadiene monomer, Grubbs ruthenium catalysts as raw material, is adopted
It is prepared from reaction and injection molding process.Dicyclopentadiene monomer is polymer grade；Catalyst is Grubbs catalyst acetic acid second
Ester solution；The mass ratio of dicyclopentadiene monomer and Grubbs ruthenium catalysts is 600:1；Injection molding reaction temperature is 35
℃.The nano imvite and kaolin (mass ratio 1:1) total addition is the 0.3% of dicyclopentadiene monomer mass, institute
The injecting forming temperature stated is 35 DEG C.
The preparation method of the modification dicyclopentadiene material of the present embodiment, comprises the following steps：
Ethyl acetate is used for solvent, Grubbs ruthenium catalysts progress ultrasonic dissolution is disperseed, Grubbs rutheniums system is formed
Catalyst acetic acid ethyl ester solution；Meanwhile, it is scattered that nano imvite, kaolin and dicyclopentadiene carry out ultrasound 2h blendings.
Grubbs ruthenium catalysts ethyl acetate solution and dicyclopentadiene nano imvite, kaolin mixture are dispersed, immediately
In-mold molding under 35 DEG C of insulations of injection, both obtains nano imvite, Modification of kaolin dicyclopentadiene material.Last batten
Processing, carries out Mechanics Performance Testing, and test result is shown in Table 3.
Embodiment 12
Dicyclopentadiene material in the present embodiment, using dicyclopentadiene monomer, Grubbs ruthenium catalysts as raw material, is adopted
It is prepared from reaction and injection molding process.Dicyclopentadiene monomer is polymer grade；Catalyst is Grubbs catalyst acetic acid second
Ester solution；The mass ratio of dicyclopentadiene monomer and Grubbs ruthenium catalysts is 600:1；Injection molding reaction temperature is 35
℃.The iron content kaolin and kaolin (mass ratio 1:1) total addition is the 0.3% of dicyclopentadiene monomer mass, institute
The injecting forming temperature stated is 35 DEG C.
The preparation method of the modification dicyclopentadiene material of the present embodiment, comprises the following steps：
Ethyl acetate is used for solvent, Grubbs ruthenium catalysts progress ultrasonic dissolution is disperseed, Grubbs rutheniums system is formed
Catalyst acetic acid ethyl ester solution；Meanwhile, it is scattered that iron content kaolin, kaolin and dicyclopentadiene carry out ultrasound 2h blendings.
Grubbs ruthenium catalysts ethyl acetate solution and dicyclopentadiene iron content kaolin, kaolin mixture are dispersed, immediately
In-mold molding under 35 DEG C of insulations of injection, both obtains iron content kaolin, Modification of kaolin dicyclopentadiene material.Last batten
Processing, carries out Mechanics Performance Testing, and test result is shown in Table 3.
Embodiment 13
Dicyclopentadiene material in the present embodiment, using dicyclopentadiene monomer, Grubbs ruthenium catalysts as raw material, is adopted
It is prepared from reaction and injection molding process.Dicyclopentadiene monomer is polymer grade；Catalyst is Grubbs catalyst acetic acid second
Ester solution；The mass ratio of dicyclopentadiene monomer and Grubbs ruthenium catalysts is 600:1；Injection molding reaction temperature is 35
℃.The glass fibre and kaolin (mass ratio 1:1) total addition is the 0.3% of dicyclopentadiene monomer mass, described
Injecting forming temperature be 35 DEG C.
The preparation method of the modification dicyclopentadiene material of the present embodiment, comprises the following steps：
Ethyl acetate is used for solvent, Grubbs ruthenium catalysts progress ultrasonic dissolution is disperseed, Grubbs rutheniums system is formed
Catalyst acetic acid ethyl ester solution；Meanwhile, it is scattered that glass fibre, kaolin and dicyclopentadiene carry out ultrasound 2h blendings.Grubbs
Ruthenium catalyst ethyl acetate solution and dicyclopentadiene glass fibre, kaolin mixture are dispersed, and 35 DEG C are injected immediately
In-mold molding under insulation, both obtains glass fibre, Modification of kaolin dicyclopentadiene material.Last batten processing, is carried out
Mechanics Performance Testing, test result is shown in Table 3.
Embodiment 14
Dicyclopentadiene material in the present embodiment, using dicyclopentadiene monomer, Grubbs ruthenium catalysts as raw material, is adopted
It is prepared from reaction and injection molding process.Dicyclopentadiene monomer is polymer grade；Catalyst is Grubbs catalyst acetic acid second
Ester solution；The mass ratio of dicyclopentadiene monomer and Grubbs ruthenium catalysts is 600:1；Injection molding reaction temperature is 35
℃.The nano imvite and glass fibre (mass ratio 1:1) total addition is the 0.3% of dicyclopentadiene monomer mass,
Described injecting forming temperature is 35 DEG C.
The preparation method of the modification dicyclopentadiene material of the present embodiment, comprises the following steps：
Ethyl acetate is used for solvent, Grubbs ruthenium catalysts progress ultrasonic dissolution is disperseed, Grubbs rutheniums system is formed
Catalyst acetic acid ethyl ester solution；Meanwhile, it is scattered that nano imvite, glass fibre and dicyclopentadiene carry out ultrasound 2h blendings.
Grubbs ruthenium catalysts ethyl acetate solution and dicyclopentadiene nano imvite, mixture of glass fibers are dispersed, stand
The in-mold molding injected under 35 DEG C of insulations, had both obtained nano imvite, glass fibre and has been modified dicyclopentadiene material.Finally
Batten is processed, and carries out Mechanics Performance Testing, and test result is shown in Table 3.
The influence being mixed into dicyclopentadiene material performance of the different carriers of table 3
Note：The mass ratio of dicyclopentadiene monomer and Grubbs ruthenium catalysts is 600:1；Forming temperature is 35 DEG C；Nothing
Machine material total content is 0.3%；It is 1 to mix both mass ratioes in inorganic material:1.
Embodiment 15
It is with dicyclopentadiene monomer, catalyst and inorganic enhancing component that the present embodiment, which is modified dicyclopentadiene material,
For raw material, it is prepared from by reaction and injection molding process, wherein, the mass ratio of dicyclopentadiene monomer and catalyst is 100:
1, the addition of inorganic enhancing component is the 0.1% of dicyclopentadiene monomer mass.
The dicyclopentadiene monomer that the present embodiment is used for polymer grade dicyclopentadiene monomer, the catalyst used for
Dual-component catalyst, the dual-component catalyst is using transition metal Ti complex compound as the first catalyst component, with Louis
This highly basic is used as the second catalyst component.Inorganic enhancing component is 1 in mass ratio by nano imvite, kaolin, iron content kaolin:
1:3 mix.
The preparation method that the present embodiment is modified dicyclopentadiene material comprises the following steps：
Step (1)：Inorganic enhancing component and dicyclopentadiene monomer are carried out into blending to disperse, it is ultrasonically treated, make inorganic increasing
Strong component is completely homogeneously dispersed in dicyclopentadiene monomer, and blend is made；
Step (2)：Obtained blend and catalyst are added sequentially in reaction injection molding reactor, are well mixed
Afterwards, in injection mould, polymerizing curable shaping is carried out, that is, described modification dicyclopentadiene material is made.
The ultrasonically treated time is 0.5 hour in step (1), and ultrasonically treated temperature is 25 DEG C, and supersonic frequency is 35KHz,
Ultrasonic power is 100W.
The temperature that polymerizing curable is molded in step (2) is 25 DEG C, and injection speed is 10mL per second, and injection pressure is
0.1MPa。
Embodiment 16
It is with dicyclopentadiene monomer, catalyst and inorganic enhancing component that the present embodiment, which is modified dicyclopentadiene material,
For raw material, it is prepared from by reaction and injection molding process, wherein, the mass ratio of dicyclopentadiene monomer and catalyst is 800:
1, the addition of inorganic enhancing component is the 1% of dicyclopentadiene monomer mass.
The dicyclopentadiene monomer that the present embodiment is used for polymer grade dicyclopentadiene monomer, the catalyst used for
Dual-component catalyst, the dual-component catalyst is using transition metal Mo complex compound as the first catalyst component, with Louis
This highly basic is used as the second catalyst component.Inorganic enhancing component is glass fibre.
The preparation method that the present embodiment is modified dicyclopentadiene material comprises the following steps：
Step (1)：Inorganic enhancing component and dicyclopentadiene monomer are carried out into blending to disperse, it is ultrasonically treated, make inorganic increasing
Strong component is completely homogeneously dispersed in dicyclopentadiene monomer, and blend is made；
Step (2)：Obtained blend and catalyst are added sequentially in reaction injection molding reactor, are well mixed
Afterwards, in injection mould, polymerizing curable shaping is carried out, that is, described modification dicyclopentadiene material is made.
The ultrasonically treated time is 3 hours in step (1), and ultrasonically treated temperature is 60 DEG C, and supersonic frequency is 53KHz, is surpassed
Acoustical power is 250W.
The temperature that polymerizing curable is molded in step (2) is 50 DEG C, and injection speed is 150mL per second, and injection pressure is
1.2MPa。
Embodiment 17
It is with dicyclopentadiene monomer, catalyst and inorganic enhancing component that the present embodiment, which is modified dicyclopentadiene material,
For raw material, it is prepared from by reaction and injection molding process, wherein, the mass ratio of dicyclopentadiene monomer and catalyst is 400:
1, the addition of inorganic enhancing component is the 0.8% of dicyclopentadiene monomer mass.
The dicyclopentadiene monomer that the present embodiment is used for polymer grade dicyclopentadiene monomer, the catalyst used for
Dual-component catalyst, the dual-component catalyst is using transition metal Ni compound as the first catalyst component, with Louis
This highly basic is used as the second catalyst component.Inorganic enhancing component is glass fibre.
The preparation method that the present embodiment is modified dicyclopentadiene material comprises the following steps：
Step (1)：Inorganic enhancing component and dicyclopentadiene monomer are carried out into blending to disperse, it is ultrasonically treated, make inorganic increasing
Strong component is completely homogeneously dispersed in dicyclopentadiene monomer, and blend is made；
Step (2)：Obtained blend and catalyst are added sequentially in reaction injection molding reactor, are well mixed
Afterwards, in injection mould, polymerizing curable shaping is carried out, that is, described modification dicyclopentadiene material is made.
The ultrasonically treated time is 1.5 hours in step (1)；The temperature that polymerizing curable is molded in step (2) is 42 DEG C.
The ultrasonically treated time is 1.5 hours in step (1), and ultrasonically treated temperature is 45 DEG C, and supersonic frequency is 53KHz,
Ultrasonic power is 150W.
The temperature that polymerizing curable is molded in step (2) is 35 DEG C, and injection speed is 120mL per second, and injection pressure is
1.0.MPa。
Claims (10)
1. a kind of modified dicyclopentadiene material, it is characterised in that the material be with dicyclopentadiene monomer, catalyst and
Inorganic enhancing component is raw material, is prepared from by reaction and injection molding process, wherein, described dicyclopentadiene monomer is with urging
The mass ratio of agent is 100-800:1, the addition of described inorganic enhancing component is the 0.1- of dicyclopentadiene monomer mass
1%.
2. a kind of modified dicyclopentadiene material according to claim 1, it is characterised in that described dicyclopentadiene
Monomer is polymer grade dicyclopentadiene monomer.
3. a kind of modified dicyclopentadiene material according to claim 1, it is characterised in that described catalyst includes
One kind in bicomponent catalyst or single component catalyst.
4. a kind of modified dicyclopentadiene material according to claim 3, it is characterised in that described bi-component catalysis
Agent is, using the compound or complex compound of transition metal as the first catalyst component, the second catalysis group to be used as using Louis's highly basic
Point.
5. a kind of modified dicyclopentadiene material according to claim 4, it is characterised in that described transition metal member
Element includes one kind in Ti, Ni, Mo or Ru.
6. a kind of modified dicyclopentadiene material according to claim 3, it is characterised in that described one pack system catalysis
Agent is the monomolecular catalytic agent containing metal carbene.
7. a kind of modified dicyclopentadiene material according to claim 1, it is characterised in that described inorganic enhancing group
Dividing includes the one or more in nano imvite, kaolin, iron content kaolin or glass fibre.
8. a kind of preparation method of modified dicyclopentadiene material as described in any one of claim 1 to 7, its feature exists
In this method specifically includes following steps：
Step (1)：Inorganic enhancing component and dicyclopentadiene monomer are carried out into blending to disperse, it is ultrasonically treated, make inorganic enhancing group
Divide and be completely homogeneously dispersed in dicyclopentadiene monomer, blend is made；
Step (2)：Obtained blend and catalyst are added sequentially in reaction injection molding reactor, after being well mixed,
Inject in mould, carry out polymerizing curable shaping, that is, described modification dicyclopentadiene material is made.
9. a kind of preparation method of modified dicyclopentadiene material according to claim 8, it is characterised in that step
(1) the ultrasonically treated time is 0.5-3 hours in.
10. a kind of preparation method of modified dicyclopentadiene material according to claim 8, it is characterised in that step
(2) temperature that polymerizing curable is molded in is 25-50 DEG C.
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| CN112961279A (en) * | 2021-02-10 | 2021-06-15 | 浙江沪通模具有限公司 | Polytrieopentadiene PTCPD and polydicyclopentadiene PDCPD copolymer and preparation method thereof |
| RU2794495C1 (en) * | 2022-01-31 | 2023-04-19 | Публичное акционерное общество "Нефтяная компания "Роснефть" (ПАО "НК "Роснефть") | Binder based on dicyclopentadiene for manufacture of polymer composite products by winding and method for its production |
| CN115895160A (en) * | 2022-12-28 | 2023-04-04 | 东实汽车科技集团股份有限公司 | Polyester fiber reinforced polydicyclopentadiene composite material and preparation method thereof |
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