CN115894869A - Thermosetting crosslinked resin and preparation method thereof - Google Patents
Thermosetting crosslinked resin and preparation method thereof Download PDFInfo
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- CN115894869A CN115894869A CN202211248043.2A CN202211248043A CN115894869A CN 115894869 A CN115894869 A CN 115894869A CN 202211248043 A CN202211248043 A CN 202211248043A CN 115894869 A CN115894869 A CN 115894869A
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- 239000011347 resin Substances 0.000 title claims abstract description 38
- 229920005989 resin Polymers 0.000 title claims abstract description 38
- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000011984 grubbs catalyst Substances 0.000 claims abstract description 45
- PNPBGYBHLCEVMK-UHFFFAOYSA-N benzylidene(dichloro)ruthenium;tricyclohexylphosphanium Chemical compound Cl[Ru](Cl)=CC1=CC=CC=C1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1 PNPBGYBHLCEVMK-UHFFFAOYSA-N 0.000 claims abstract description 43
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims abstract description 33
- 238000004132 cross linking Methods 0.000 claims abstract description 14
- 239000003999 initiator Substances 0.000 claims abstract description 13
- 150000003254 radicals Chemical class 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 7
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 19
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 15
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 15
- OJOWICOBYCXEKR-KRXBUXKQSA-N (5e)-5-ethylidenebicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(=C/C)/CC1C=C2 OJOWICOBYCXEKR-KRXBUXKQSA-N 0.000 claims description 12
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 claims description 10
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 10
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- 235000006708 antioxidants Nutrition 0.000 claims description 6
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 claims description 6
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 claims description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 5
- NSTVHFOHEYKXRQ-UHFFFAOYSA-N 4-bicyclo[2.2.1]hept-2-enylmethanol Chemical compound C1CC2C=CC1(CO)C2 NSTVHFOHEYKXRQ-UHFFFAOYSA-N 0.000 claims description 5
- INYHZQLKOKTDAI-UHFFFAOYSA-N 5-ethenylbicyclo[2.2.1]hept-2-ene Chemical compound C1C2C(C=C)CC1C=C2 INYHZQLKOKTDAI-UHFFFAOYSA-N 0.000 claims description 5
- 239000004593 Epoxy Substances 0.000 claims description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 5
- CHWKGJOTGCSFNF-UHFFFAOYSA-N norbornene anhydride Chemical compound C1CC2C3C(=O)OC(=O)C3=C1C2 CHWKGJOTGCSFNF-UHFFFAOYSA-N 0.000 claims description 5
- IMOYOUMVYICGCA-UHFFFAOYSA-N 2-tert-butyl-4-hydroxyanisole Chemical compound COC1=CC=C(O)C=C1C(C)(C)C IMOYOUMVYICGCA-UHFFFAOYSA-N 0.000 claims description 4
- KOKLYLSZOGGBHE-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-4-carbonitrile Chemical compound C1CC2C=CC1(C#N)C2 KOKLYLSZOGGBHE-UHFFFAOYSA-N 0.000 claims description 4
- FYGUSUBEMUKACF-UHFFFAOYSA-N bicyclo[2.2.1]hept-2-ene-5-carboxylic acid Chemical compound C1C2C(C(=O)O)CC1C=C2 FYGUSUBEMUKACF-UHFFFAOYSA-N 0.000 claims description 4
- URYYVOIYTNXXBN-UPHRSURJSA-N cyclooctene Chemical compound C1CCC\C=C/CC1 URYYVOIYTNXXBN-UPHRSURJSA-N 0.000 claims description 4
- 239000004913 cyclooctene Substances 0.000 claims description 4
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 229940087305 limonene Drugs 0.000 claims description 3
- 235000001510 limonene Nutrition 0.000 claims description 3
- -1 pinene Chemical compound 0.000 claims description 3
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 2
- 239000011342 resin composition Substances 0.000 claims 1
- 229920001153 Polydicyclopentadiene Polymers 0.000 abstract description 43
- 238000006116 polymerization reaction Methods 0.000 abstract description 34
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 230000009477 glass transition Effects 0.000 description 61
- 239000000047 product Substances 0.000 description 36
- 238000006243 chemical reaction Methods 0.000 description 31
- 238000002156 mixing Methods 0.000 description 21
- 229920000642 polymer Polymers 0.000 description 18
- 238000005303 weighing Methods 0.000 description 15
- 238000005259 measurement Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- FPAZNLSVMWRGQB-UHFFFAOYSA-N 1,2-bis(tert-butylperoxy)-3,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(OOC(C)(C)C)C(OOC(C)(C)C)=C1C(C)C FPAZNLSVMWRGQB-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 6
- 230000000379 polymerizing effect Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000007142 ring opening reaction Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004634 thermosetting polymer Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 2
- 238000011066 ex-situ storage Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000010526 radical polymerization reaction Methods 0.000 description 2
- 238000007348 radical reaction Methods 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- FCHGUOSEXNGSMK-UHFFFAOYSA-N 1-tert-butylperoxy-2,3-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC(OOC(C)(C)C)=C1C(C)C FCHGUOSEXNGSMK-UHFFFAOYSA-N 0.000 description 1
- 239000004278 EU approved seasoning Substances 0.000 description 1
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- 230000015572 biosynthetic process Effects 0.000 description 1
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- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000000396 limonene group Chemical group 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The invention discloses thermosetting cross-linked resin and a preparation method thereof, wherein a mixture of dicyclopentadiene, a regulator, a Grubbs catalyst, a free radical initiator and an antioxidant is taken; the mixture reacts at-15 to 50 ℃ to generate thermosetting crosslinking resin. The preparation method can realize the rapid manufacture of the sample under the low-temperature condition and meet certain use requirements. And the high-performance continuous polymerization of the polydicyclopentadiene can be realized through subsequent heat treatment, so that the high-performance polydicyclopentadiene resin can be obtained.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to thermosetting crosslinked resin and a preparation method thereof.
Background
Dicyclopentadiene (DCPD) is a compound containing two cyclic double bonds, is a byproduct in petrochemical industry, and has high yield. The ring double bond of dicyclopentadiene has chemical activity, and can be subjected to ring-opening ectopic polymerization to obtain polydicyclopentadiene. The polydicyclopentadiene is a thermosetting polymer with excellent performance, has the advantages of good mechanical property, good light transmission, good dielectric property, good chemical corrosion resistance and the like, and can be used for preparing composite materials, chemical equipment, electronic equipment and the like.
Disclosure of Invention
The application adopts a sequential polymerization method, provides a finished product which can be rapidly molded, and the finished product can meet a certain use requirement and can further realize high performance of the product through subsequent curing so as to meet another use requirement. Therefore, the method can not only rapidly manufacture the parts meeting certain use requirements, but also improve the performance of the products through subsequent reshaping or post-treatment, and can greatly widen the application range of the polydicyclopentadiene.
The present application provides the following methods to achieve the above object:
a thermosetting cross-linked resin is prepared from dicyclopentadiene, regulator, grubbs catalyst, free radical initiator and antioxidant through mixing; the mixture reacts at-10-50 ℃ to generate thermosetting crosslinking resin.
According to some preferred embodiments of the present invention, the modifier is selected from one or a combination of two or more of norbornene, norbornadiene, cyanonorbornene, norbornene carboxylic acid, norbornene anhydride, norbornene methanol, ethylidene norbornene, vinyl norbornene, epoxy norbornene, pinene, cyclooctene, cyclooctadiene, limonene.
According to some preferred embodiments of the present invention, the modifier is selected from any one or a combination of two or more of norbornene, norbornadiene, norbornene methanol, ethylidene norbornene, norbornene anhydride, epoxy norbornene, vinyl norbornene, pinene.
The molecular weight regulator has the following structural formula:
norbornene has the structural formula:
norbornadiene has the structural formula:
the structural formula of the norbornene methanol is as follows:
the structural formula of ethylidene norbornene is as follows:
norbornene anhydride has the structural formula:
the structural formula of the epoxy norbornene is as follows:
the structural formula of the vinyl norbornene is as follows:
the structural formula of pinene is:
the cyano norbornene has the formula:
norbornene carboxylic acid has the formula:
the cyclooctene has the formula:
the cyclooctadiene has the formula:
the limonene structure formula is:
according to some preferred embodiments of the present invention, the radical initiator is selected from one or a combination of two or more of azobisisobutyronitrile, benzoyl peroxide, dicumyl peroxide, 1-di-t-butylperoxycyclohexane and di-t-butylperoxydiisopropylbenzene.
According to some preferred embodiments of the present invention, the antioxidant is selected from any one or a combination of two or more of 2, 6-di-tert-butyl-4-methylphenol, tert-butyl-4-hydroxyanisole, methylhydroquinone and ascorbic acid.
According to some preferred embodiments of the present invention, the components are used in the following amounts in parts by weight: 8-100 parts of dicyclopentadiene, 0.1-60 parts of regulator, 0.05-2 parts of Grubbs catalyst, 0.1-5 parts of free radical initiator and 0.1-1 part of antioxidant.
According to some preferred embodiments of the invention, the catalyst is selected from Grubbs catalysts. The structural formulas of the Grubbs series catalysts are listed as follows, the Grubbs series catalysts are respectively named as Grubbs catalyst 1, grubbs catalyst 2, grubbs catalyst 3, grubbs catalyst 4, grubbs catalyst 5, grubbs catalyst 6, grubbs catalyst 7 and Grubbs catalyst 8, only part of the Grubbs series catalysts are listed in the application, and Grubbs catalysts with other structural formulas can also be applied to the application. The structural formula of each catalyst is as follows:
grubbs catalyst 1 has the structural formula:
grubbs catalyst 2 has the structural formula:
grubbs catalyst 3 has the structural formula:
grubbs catalyst 4 has the structural formula:
grubbs catalyst 5 has the structural formula:
grubbs catalyst 6 has the structural formula:
grubbs catalyst 7 has the structural formula:
the structural formula of Grubbs catalyst 8 is:
the invention provides a thermosetting crosslinked resin which is prepared by any one of the preparation methods of the thermosetting crosslinked resin.
The invention also provides another preparation method of the thermosetting cross-linked resin, which takes the cross-linked thermosetting resin to react at the temperature of more than 180 ℃ to generate the thermosetting cross-linked resin. The invention also provides a cross-linked thermosetting resin, and the reinforced thermosetting cross-linked resin is obtained by adopting the further reaction. Here, "above" includes the original number of 180 ℃.
The thermosetting cross-linked resin prepared by the method can be used as a base resin, and other seasonings, modifiers and the like can be added according to actual application requirements, so that special modified resin products meeting various terminal requirements can be obtained. For example, in the preparation of the fiber composite material, liquid resin and fiber are mixed and then react quickly at low temperature to obtain a product with a specific shape, and then the temperature is raised in an oven to improve the performance.
The beneficial effects of the invention are:
the invention can realize the rapid manufacture of the sample under the condition of low temperature and meet certain use requirements. And the high-performance continuous polymerization of the polydicyclopentadiene can be realized through subsequent heat treatment, so that the high-performance polydicyclopentadiene resin is obtained, the glass transition temperature of the resin is greatly improved, and the application range of the resin is wider.
Drawings
FIG. 1 is a graph of the glass transition temperature of a resin prepared using example 1 in accordance with the present invention;
FIG. 2 is a graph of the glass transition temperature of a resin prepared using example 2 in accordance with the present invention;
FIG. 3 is a graph showing the glass transition temperature of a resin prepared by using example 3 according to the present invention 。
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. The components of the embodiments of the present invention, as generally described and illustrated in the figures herein, may be arranged and designed in a wide variety of different configurations.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
According to the application, a Grubbs catalyst is used as a catalyst for ring-opening ex-situ polymerization, and DCPD can be polymerized into polydicyclopentadiene under the action of the Grubbs catalyst based on the characteristic of ring-opening ex-situ polymerization. However, the chemical structure of DCPD has a cyclopentene structure with low activity, which is difficult to undergo ring-opening polymerization, resulting in low crosslinking density of polydicyclopentadiene, and poor dielectric properties, heat resistance, mechanical properties, etc.
Further analysis of the chemical structure of polydicyclopentadiene reveals that the polymer has double bonds and free radical crosslinking reaction can occur. If the double bonds of polydicyclopentadiene can be subjected to a crosslinking reaction through a free radical reaction, the crosslinking density of polydicyclopentadiene can be increased, and the performance of polydicyclopentadiene can be improved. However, the radical reaction generally requires a long time at a relatively high temperature, and does not allow rapid production of the product.
Sequential polymerization is a method for synthesizing polymers by combining different polymerization methods, and can be used for synthesizing polymers with complex structures and high performance. When the polymer is synthesized by adopting a sequential polymerization method, a proper polymerization method and an initiator are selected, different groups are sequentially initiated to generate polymerization reaction by controlling a polymerization process, and the polymerization reaction is sequentially carried out according to a pre-designed reaction sequence, so that the high-performance polymer is finally prepared. The key to sequential polymerization is how compatible the corresponding initiators, catalysts and monomers are selected and how the interactions among the polymerization reactions are small, so that the sequential polymerization method is not easy to realize, especially the synthesis of thermosetting polymers. Since thermosetting polymers are difficult to dissolve in solvents and difficult to melt by heating, monomers are mixed with initiators, catalysts and the like at one time before polymerization, and sequential polymerization is realized by a controlled process. The polydicyclopentadiene obtained by ring-opening heterotopic polymerization is a cross-linked structure, so sequential polymerization cannot be realized by a method of subsequently adding an initiator, a catalyst or a monomer, but DCPD, the initiator, the catalyst and the like can be blended at one time, and then sequential polymerization is realized by controlling a polymerization process.
The application finally obtains a set of sequential polymerization method through a great deal of creative experiments, and also finds that: if the first polymerization step is insufficient, a large amount of DCPD may remain. DCPD decomposes to cyclopentadiene at elevated temperatures, which has very low chemical activity and is not amenable to ring-opening metathesis and free radical polymerization. Furthermore, the cyclopentadiene has a low boiling point (about 41.5 ℃), which causes a large number of holes in the product, resulting in a large number of defects, and thus the product cannot meet the actual use requirements. In addition, when the first step reaction is found to be insufficient by a large number of failure cases, i.e., high-temperature treatment, decomposition products of the radical initiator may deactivate the Grubbs catalyst, and ring-opening polymerization may not be performed, and more DCPD may remain.
In particular, the present application demonstrates the reliability of the sequential polymerization process employed by the present application by way of the following examples.
The room temperature described in the following examples, generally referred to as about 25 ℃, may be different for different seasonal conditions, but the components may be adjusted to some extent so that they can react at room temperature; or kept at about 25 ℃ by adjusting the room temperature. The selection of a temperature of 25 ℃ is not intended to indicate that the reaction can be carried out only at this temperature, but rather at lower temperatures, such as-15 ℃, -10 ℃, -5 ℃, 0 ℃,5 ℃, or higher temperatures, such as 30 ℃,35 ℃,40 ℃,50 ℃.
The test specimens usable in the present application can be prepared into dumbbell, strip, and sheet (100 mm. Times.100 mm. Times.2 mm) for testing.
The second round of reaction at higher temperature can raise the glass transition temperature of the product, thereby meeting higher use requirements. Research experiments and researches of the inventor show that the product finally prepared at the reaction temperature of 180 ℃ can meet the use requirements, and in the further research process, the improvement of the reaction temperature is beneficial to the increase of the glass transition temperature, so that the performance of the product can be further improved, and particularly, after the reaction temperature reaches 200 ℃, the improvement of the glass transition temperature is obviously higher than the glass transition temperature of the product prepared by the reaction at the temperature lower than 200 ℃. The reaction temperature is higher than 200 deg.C, such as 220 deg.C, 230 deg.C, 240 deg.C, 250 deg.C, 260 deg.C, 265 deg.C, 280 deg.C, etc., and higher. The second round of reaction temperature can be selected according to specific needs, such as only one temperature-rising reaction, two temperature-rising reactions, and more temperature-rising reactions. The reaction temperature can be any temperature above 180 ℃. In further practical production, the mode of heating twice or more is beneficial to improving the comprehensive performance of the prepared product, and the preparation is mainly carried out by adopting the mode of heating twice for reaction, such as the reaction combination of 200 ℃ and 250 ℃, based on the convenience of process adjustment. The combination of properties refers to the set of physical properties such as tensile strength, tensile modulus, impact strength, etc., except for glass transition temperature.
The higher temperature reaction examples are not noted in this application and do not represent products prepared by the reaction above 250 ℃ according to the embodiments of the present application. In practical application, higher temperatures of 255 ℃, 260 ℃, 265 ℃, 270 ℃, 275 ℃, 280 ℃, 285 ℃, 290 ℃,300 ℃ and the like can be selected, but based on comprehensive consideration of practical production, the selection of an economical reaction condition is a better choice, such as 250 ℃. The method adopts a one-time heating reaction mode, such as directly reacting at 200 ℃, 220 ℃, 240 ℃,250 ℃, 260 ℃, 265 ℃, 280 ℃ and higher temperature.
The radical polymerization reaction in the embodiments of the present application is selected to be 6 hours, mainly to ensure complete reaction, i.e., to reserve enough reaction time, and practical embodiments may react completely in a shorter time, such as 3 hours, 2.5 hours, 2 hours, 1.5 hours, or a shorter time, such as 1 hour.
Example 1
Weighing 97.5 parts of dicyclopentadiene and 2.5 parts of ethylidene norbornene, and mixing to obtain a liquid at room temperature; adding 1 part of dicumyl peroxide and 0.1 part of 2, 6-di-tert-butyl-4-methylphenol, and uniformly mixing; finally, 0.1 part of Grubbs catalyst 2 was added, and the mixture was poured into a mold and reacted at 40 ℃ for 300 seconds to obtain a sample. The glass transition temperature of the sample was 176 ℃ by DMA measurement (173 ℃ by DSC measurement), and the crosslink density was calculated to be 1.4X 10 3 mol/m 3 . Measured out ofThe tensile strength of the test sample is 42Mpa, and the tensile modulus is 1.03GPa; transferring the sample into a common oven (hot press, plate vulcanizer, etc.) at 200 deg.C, standing for 3 hr, measuring by DMA that the glass transition temperature of the sample is 224 deg.C (187 deg.C by DSC), and calculating to obtain a cross-linking density of 2.6 × 10 3 mol/m 3 . Measuring the tensile strength of the sample to be 44Mpa and the tensile modulus to be 1.33GPa; after leaving at 250 ℃ for 3 hours, the glass transition temperature of the sample was 231 ℃ by DMA measurement (198 ℃ by DSC measurement), and the crosslink density was calculated to be 6.0X 10 3 mol/m 3 . The tensile strength of the test specimen was measured to be 56MPa, and the tensile modulus was measured to be 2.01GPa.
Example 2
Weighing 95 parts of dicyclopentadiene and 5 parts of ethylidene norbornene, mixing, and obtaining liquid at room temperature; adding 0.1 part of dicumyl peroxide and 0.2 part of 2, 6-di-tert-butyl-4-methylphenol, and uniformly mixing; finally, 0.2 part of Grubbs catalyst 2 was added, poured into a mold, and reacted at 50 ℃ for 300 seconds to obtain a sample. The glass transition temperature of the sample was 176 ℃ by DMA measurement (170 ℃ by DSC measurement), and the crosslink density was calculated to be 0.2X 10 3 mol/m 3 . The tensile strength of the sample is measured to be 41Mpa, and the tensile modulus is measured to be 1.14GPa; transferring the sample into a common oven (hot press, plate vulcanizer, etc.) at 200 deg.C for 3 hr, measuring by DMA the glass transition temperature of 190 deg.C (175 deg.C by DSC), and calculating to obtain a crosslinking density of 1.0 × 10 3 mol/m 3 . Measuring the tensile strength of the sample to be 42Mpa and the tensile modulus to be 1.23GPa; after standing at 250 ℃ for 3 hours, the glass transition temperature of the sample was 202 ℃ as measured by DMA (186 ℃ C. As measured by DSC), and the crosslink density was calculated to be 2.9X 10 3 mol/m 3 . The tensile strength of the test specimen was measured to be 47MPa, and the tensile modulus was measured to be 1.46GPa.
Example 3
Weighing 95 parts of dicyclopentadiene and 5 parts of ethylidene norbornene, mixing, and obtaining liquid at room temperature; adding 0.1 part of dicumyl peroxide and 1 part of 2, 6-di-tert-butyl-4-methylphenol, and uniformly mixing; finally, 0.2 part of Grubbs catalyst 2 was added, poured into a mold, and reacted at 25 ℃ for 180 seconds to obtain a sample. DMA measurement of vitrification of the sampleThe transition temperature was 171 ℃ in DSC 168 ℃ and the crosslink density was calculated to be 0.5X 10 3 mol/m 3 . Measuring the tensile strength of the test sample to be 42Mpa and the tensile modulus to be 1.01GPa; transferring the sample into a common oven (hot press, plate vulcanizer, etc.) at 200 deg.C, standing for 3 hr, measuring by DMA that the glass transition temperature of the sample is 184 deg.C (176 deg.C by DSC), and calculating to obtain a cross-linking density of 0.5 × 10 3 mol/m 3 . Measuring the tensile strength of the sample to be 43Mpa and the tensile modulus to be 1.08GPa; after standing at 250 ℃ for 3 hours, the glass transition temperature of the specimen was 198 ℃ by DMA measurement (183 ℃ by DSC measurement), and the crosslink density was calculated to be 0.8X 10 3 mol/m 3 . The tensile strength of the test specimen was found to be 46MPa, and the tensile modulus was found to be 1.23GPa.
Example 4
Weighing 90 parts of dicyclopentadiene and 10 parts of ethylidene norbornene, mixing, and obtaining liquid at room temperature; adding 1 part of di-tert-butylperoxydiisopropylbenzene and 0.1 part of 2, 6-di-tert-butyl-4-methylphenol, and uniformly mixing; finally, 0.2 part of Grubbs catalyst 2 was added, poured into a mold, and reacted at 35 ℃ for 120 seconds to obtain a sample. The glass transition temperature of the sample was 169 ℃ by DMA measurement (146 ℃ by DSC measurement), and the crosslink density was calculated to be 1.08X 10 3 mol/m 3 . Measuring the tensile strength of the sample to be 43Mpa and the tensile modulus to be 1.08GPa; after the sample was transferred into a general oven and allowed to stand at 200 ℃ for 3 hours, the glass transition temperature of the sample was measured by DMA (by DSC, 155 ℃ C.), and the crosslink density was calculated to be 1.28X 10 3 mol/m 3 . Measuring the tensile strength of the sample to be 46Mpa and the tensile modulus to be 1.46GPa; after standing at 250 ℃ for 3 hours, the glass transition temperature of the sample was 202 ℃ as measured by DMA (168 ℃ as measured by DSC) and the crosslink density was calculated to be 3.29X 10 3 mol/m 3 . The tensile strength of the test specimen was measured to be 51MPa, and the tensile modulus was measured to be 1.83GPa.
Example 5
Weighing 80 parts of dicyclopentadiene and 20 parts of ethylidene norbornene, and mixing to obtain a liquid at the temperature of-10 ℃; adding 1 part of dicumyl peroxide and 0.2 part of 2, 6-di-tert-butyl-4-methylphenol, and uniformly mixing; finally, 0.2 part of Grubbs catalyst 2 was added, and the mixture was poured into a mold and reacted at-10 ℃ for 60 minutes to obtain a sample. The glass transition temperature of the sample was measured by DMA to be 140 ℃. The tensile strength of the sample is measured to be 49Mpa, and the tensile modulus is measured to be 1.14GPa; the sample is transferred into a common oven (a hot press, a flat vulcanizing machine and the like can be selected as well), and after the sample is placed for 3 hours at 200 ℃, the glass transition temperature of the sample is 174 ℃ measured by DMA. The tensile strength of the sample is measured to be 51Mpa, and the tensile modulus is measured to be 1.43GPa; after 3 hours at 250 ℃, the glass transition temperature of the sample was determined to be 197 ℃ by DMA. The tensile strength of the test specimen was measured to be 54Mpa, and the tensile modulus to be 1.56GPa.
Examples 1-5 provide the glass transition temperature change of the resulting article after reaction of the prepared product at different temperatures, respectively. From the data, it can be seen that the glass transition temperature of the final resin product is significantly increased by carrying out the sequential polymerization reaction, and the applicants have found that the increase of the crosslinking density is not favored by the excessively low temperature during the initial reaction, and that the increase of the crosslinking density is favored by the longer time of the initial reaction.
As the glass transition temperature is an important index of the product, and the glass transition temperature of the prepared product meets the design requirement, other indexes can be used. In addition, the crosslinking density is obtained by calculation, and can only reflect the crosslinking condition of the material with the same raw material ratio, but not the performance index of the material, so the following examples mainly represent the product performance by the index of the glass transition temperature.
Example 6
100 parts of dicyclopentadiene, 0.1 part of norbornene, 5 parts of azobisisobutyronitrile and 1 part of ascorbic acid are weighed and mixed uniformly. 2 parts of Grubbs catalyst 1 were added and mixed rapidly. At 50 ℃, polymerizing for 180 seconds to obtain polydicyclopentadiene, wherein the glass transition temperature of the product is 174 ℃, and the use requirement of the product can be met.
The obtained polydicyclopentadiene is reacted for 3 hours at 200 ℃ and for 3 hours at 250 ℃, and the glass transition temperature of the polydicyclopentadiene can be raised to 202 ℃.
Example 7
Weighing 40 parts of dicyclopentadiene, 60 parts of norbornadiene, 1 part of dicumyl peroxide and 0.5 part of methyl hydroquinone, and uniformly mixing. 1 part of Grubbs catalyst 2 was added and mixed rapidly. At 0 ℃, the polydicyclopentadiene is obtained after 600 seconds of polymerization, and the glass transition temperature of the product is 92 ℃.
The glass transition temperature of the polydicyclopentadiene can be raised to 184 ℃ by reacting the polymer at 200 ℃ for 3 hours and at 250 ℃ for 3 hours.
Example 8
95 parts of dicyclopentadiene, 5 parts of cyanonorbornene, 1 part of dicumyl peroxide and 0.5 part of methylhydroquinone are weighed out and mixed uniformly. 0.5 part Grubbs catalyst 3 was added and mixed rapidly. At 25 ℃, the polydicyclopentadiene is obtained after polymerization within 300 seconds, and the glass transition temperature of the product is 131 ℃.
The glass transition temperature of the polydicyclopentadiene can be raised to 178 ℃ by reacting the polymer at 200 ℃ for 3 hours and at 250 ℃ for 3 hours.
Example 9
95 parts of dicyclopentadiene, 5 parts of norbornene carboxylic acid, 0.1 part of bis-tert-butylperoxydiisopropylbenzene and 1 part of 2, 6-di-tert-butyl-4-methylphenol are weighed and mixed uniformly. 0.5 part of Grubbs catalyst 4 was added and mixed rapidly. At 40 ℃, the polydicyclopentadiene is obtained after polymerization within 300 seconds, and the glass transition temperature of the product is 183 ℃.
The glass transition temperature of the polydicyclopentadiene can be raised to 197 ℃ by reacting the polymer at 200 ℃ for 3 hours and at 250 ℃ for 3 hours.
Example 10
Weighing 95 parts of dicyclopentadiene, 5 parts of norbornene anhydride, 0.5 part of bis-tert-butylperoxydiisopropylbenzene, 0.5 part of dicumyl peroxide and 0.1 part of tert-butyl-4-hydroxyanisole, and uniformly mixing. 0.05 part of Grubbs catalyst 5 was added and mixed rapidly. At 50 ℃, the polydicyclopentadiene is obtained after 600 seconds of polymerization, and the glass transition temperature of the product is 176 ℃.
The glass transition temperature of polydicyclopentadiene can be raised to 224 ℃ by reacting the polymer at 200 ℃ for 3 hours and 250 ℃ for 3 hours.
Example 11
Weighing 98 parts of dicyclopentadiene, 2 parts of norbornene methanol, 2 parts of bis-tert-butylperoxydiisopropyl benzene and 0.1 part of tert-butyl-4-hydroxy anisole, and uniformly mixing. 0.1 part Grubbs catalyst 7 was added and mixed rapidly. At 10 ℃, the polydicyclopentadiene is obtained after polymerization within 300 seconds, and the glass transition temperature of the product is 168 ℃.
The glass transition temperature of the polydicyclopentadiene can be raised to 197 ℃ by reacting the polymer at 200 ℃ for 3 hours and at 250 ℃ for 3 hours.
Example 12
Weighing 95 parts of dicyclopentadiene, 5 parts of epoxy norbornene, 1 part of bis (tert-butylperoxydiisopropylbenzene) and 0.1 part of 2, 6-di-tert-butyl-4-methylphenol, and uniformly mixing. 0.1 part Grubbs catalyst 7 was added and mixed rapidly. At 40 ℃, the polydicyclopentadiene is obtained by polymerization for 10 seconds, and the glass transition temperature of the product is 131 ℃.
The glass transition temperature of the polydicyclopentadiene can be raised to 184 ℃ by reacting the polymer at 200 ℃ for 3 hours and at 250 ℃ for 3 hours.
Example 13
Weighing 90 parts of dicyclopentadiene, 10 parts of pinene, 1 part of bis-tert-butylperoxydiisopropylbenzene and 0.1 part of 2, 6-di-tert-butyl-4-methylphenol, and uniformly mixing. 0.2 part Grubbs catalyst 8 was added and mixed rapidly. At 40 ℃, polymerizing for 30 seconds to obtain polydicyclopentadiene, wherein the glass transition temperature of the product is 122 ℃.
The glass transition temperature of polydicyclopentadiene can be raised to 184 ℃ by reacting the polymer at 250 ℃ for 3 hours.
Example 14
Weighing 95 parts of dicyclopentadiene, 5 parts of cyclooctene, 1 part of bis-tert-butylperoxydiisopropylbenzene and 0.1 part of 2, 6-di-tert-butyl-4-methylphenol, and uniformly mixing. 0.2 part of Grubbs catalyst 8 was added and mixed rapidly. At 25 ℃, the polydicyclopentadiene is obtained by polymerization for 30 seconds, and the glass transition temperature of the product is 167 ℃.
The glass transition temperature of polydicyclopentadiene can be raised to 196 ℃ by reacting the polymer at 200 ℃ for 3 hours and 250 ℃ for 3 hours.
Example 15
Weighing 8 parts of dicyclopentadiene, 5 parts of limonene, 1 part of 1, 1-di-tert-butyl peroxycyclohexane and 0.1 part of methyl hydroquinone, and uniformly mixing. 0.5 part of Grubbs catalyst 8 was added and mixed rapidly. Polymerizing for 300 seconds at 40 ℃ to obtain polydicyclopentadiene, wherein the glass transition temperature of the product is 167 ℃.
The glass transition temperature of polydicyclopentadiene can be raised to 189 ℃ by reacting the polymer at 200 ℃ for 3 hours and 250 ℃ for 3 hours.
Example 16
Weighing 40 parts of dicyclopentadiene, 60 parts of ethylidene norbornene, 0.5 part of bis-tert-butylperoxydiisopropylbenzene and 0.1 part of 2, 6-di-tert-butyl-4-methylphenol, and uniformly mixing. 0.2 part of Grubbs catalyst 3 was added and mixed rapidly. At 25 ℃, the polydicyclopentadiene is obtained by polymerization for 15 seconds, and the glass transition temperature of the product is 109 ℃.
The glass transition temperature of the polydicyclopentadiene can be raised to 144 ℃ by reacting the polymer at 200 ℃ for 3 hours and at 250 ℃ for 3 hours.
Example 17
Weighing 80 parts of dicyclopentadiene, 10 parts of ethylidene norbornene, 10 parts of vinyl norbornene, 0.5 part of bis-tert-butylperoxydiisopropylbenzene and 0.1 part of 2, 6-di-tert-butyl-4-methylphenol, and uniformly mixing. 0.2 part of Grubbs catalyst 3 was added and mixed rapidly. Polymerizing for 180 seconds at 50 ℃ to obtain polydicyclopentadiene, wherein the glass transition temperature of the product is 125 ℃.
The glass transition temperature of the polydicyclopentadiene can be raised to 144 ℃ by reacting the polymer at 200 ℃ for 3 hours and at 250 ℃ for 3 hours.
Example 18
Weighing 80 parts of dicyclopentadiene, 20 parts of norbornadiene, 1 part of bis-tert-butylperoxydiisopropylbenzene and 0.1 part of 2, 6-di-tert-butyl-4-methylphenol, and uniformly mixing. 0.2 part of Grubbs catalyst 8 was added and mixed rapidly. Polymerizing for 5 seconds at the temperature of 20 ℃ to obtain polydicyclopentadiene, wherein the glass transition temperature of the product is 92 ℃.
The glass transition temperature of polydicyclopentadiene can be raised to 186 ℃ by reacting the polymer at 250 ℃ for 3 hours.
In the comparative examples, unless otherwise specified, the raw materials and the amounts thereof were the same as those in the corresponding examples; the two-step reaction, if not otherwise specified, the first-step reaction conditions or the second-step reaction conditions were also the same as those in the corresponding examples. As the sample tested by DMA is a sample which is free from defects or has few defects observed by naked eyes, the samples prepared by the comparative examples have a large amount of bubbles, the sample with few defects cannot be prepared, and the DSC test is adopted if the requirements of the test are not met.
Comparative example 1
97.5 parts of dicyclopentadiene, 2.5 parts of ethylidene norbornene, 0.1 part of bis-tert-butylperoxydiisopropylbenzene and 0.1 part of 2, 6-di-tert-butyl-4-methylphenol are weighed and mixed uniformly. 0.1 part of Grubbs catalyst 3 was added and mixed rapidly. Polymerizing for 5 seconds at 50 ℃ to obtain polydicyclopentadiene, wherein the glass transition temperature of the product is 90 ℃.
The polymer was reacted at 200 ℃ for 3 hours and 250 ℃ for 3 hours, and the glass transition temperature of polydicyclopentadiene was raised to 117 ℃.
Comparative example 2
Comparative example 2 has the same raw material ratio as example 2. When the raw materials are mixed uniformly and directly placed in a common oven at 250 ℃, only a sample with a large number of foam holes can be obtained. The glass transition temperature of the sample was determined by DSC to be 79 ℃.
Comparative example 3
Comparative example 3 has the same raw material ratio as example 1. After the raw materials are mixed uniformly, the mixture is placed in a common oven at 200 ℃, and only a sample with a large number of foam holes can be obtained. The glass transition temperature of the sample was 79 ℃ as measured by DSC; the reaction was carried out at 250 ℃ for 3 hours, and the glass transition temperature of the sample was 94 ℃.
Comparative example 4
Comparative example 4 has the same raw material ratio as example 4. After the raw materials are uniformly mixed, the mixture is placed in a common oven at 150 ℃, and only a sample with a large number of cells can be obtained. The glass transition temperature of the sample measured by DSC is 23 ℃; the reaction was carried out at 250 ℃ for 3 hours, and the glass transition temperature of the sample was 36 ℃.
The above examples are only intended to illustrate the technical solution of the present invention, and not to limit it; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (8)
1. A method for preparing thermosetting cross-linked resin is characterized in that a mixture of dicyclopentadiene, a regulator, a Grubbs catalyst, a free radical initiator and an antioxidant is taken; the mixture reacts at-15 to 50 ℃ to generate thermosetting crosslinking resin.
2. The method for producing a thermosetting crosslinked resin according to claim 1, characterized in that: the regulator is selected from one or the combination of more than two of norbornene, norbornadiene, cyano norbornene, norbornene carboxylic acid, norbornene anhydride, norbornene methanol, ethylidene norbornene, vinyl norbornene, epoxy norbornene, pinene, cyclooctene, cyclooctadiene and limonene.
3. The method for producing a thermosetting crosslinked resin according to claim 1, characterized in that: the free radical initiator is one or the combination of more than two of azodiisobutyronitrile, benzoyl peroxide, dicumyl peroxide, 1-di-tert-butyl peroxycyclohexane and di-tert-butyl peroxydiisopropylbenzene.
4. The method for producing a thermosetting crosslinked resin according to claim 1, characterized in that: the antioxidant is selected from any one or combination of more than two of 2, 6-di-tert-butyl-4-methylphenol, tert-butyl-4-hydroxyanisole, methyl hydroquinone and ascorbic acid.
5. The method for preparing thermosetting crosslinked resin according to claim 1, wherein the components are used in the following amounts in parts by weight: 8-100 parts of dicyclopentadiene, 0.1-60 parts of regulator, 0.05-2 parts of Grubbs catalyst, 0.1-5 parts of free radical initiator and 0.1-1 part of antioxidant.
6. A crosslinked thermosetting resin characterized by: prepared by the method for preparing thermosetting crosslinked resin according to any one of claims 1 to 5.
7. A method for preparing thermosetting crosslinked resin is characterized in that: a cross-linked thermosetting resin according to claim 6, which is reacted at a temperature of 180 ℃ or higher to give a thermosetting cross-linked resin.
8. A crosslinked thermosetting resin characterized by: the thermosetting crosslinked resin composition according to claim 7.
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