CN110591000B - High-temperature-resistant die material of poly-dicyclopentadienyl and preparation method thereof - Google Patents
High-temperature-resistant die material of poly-dicyclopentadienyl and preparation method thereof Download PDFInfo
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- CN110591000B CN110591000B CN201910928882.0A CN201910928882A CN110591000B CN 110591000 B CN110591000 B CN 110591000B CN 201910928882 A CN201910928882 A CN 201910928882A CN 110591000 B CN110591000 B CN 110591000B
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- 239000000463 material Substances 0.000 title claims abstract description 31
- IZSHZLKNFQAAKX-UHFFFAOYSA-N 5-cyclopenta-2,4-dien-1-ylcyclopenta-1,3-diene Chemical group C1=CC=CC1C1C=CC=C1 IZSHZLKNFQAAKX-UHFFFAOYSA-N 0.000 title claims description 19
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 58
- 239000002994 raw material Substances 0.000 claims abstract description 57
- 229920005989 resin Polymers 0.000 claims abstract description 57
- 239000011347 resin Substances 0.000 claims abstract description 57
- 239000000945 filler Substances 0.000 claims abstract description 35
- 239000003607 modifier Substances 0.000 claims abstract description 26
- 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 23
- 239000011984 grubbs catalyst Substances 0.000 claims abstract description 23
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 14
- 239000000178 monomer Substances 0.000 claims abstract description 12
- HECLRDQVFMWTQS-UHFFFAOYSA-N Dicyclopentadiene Chemical compound C1C2C3CC=CC3C1C=C2 HECLRDQVFMWTQS-UHFFFAOYSA-N 0.000 claims abstract 6
- 239000004744 fabric Substances 0.000 claims description 32
- 239000003365 glass fiber Substances 0.000 claims description 32
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 15
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000005520 cutting process Methods 0.000 claims description 10
- 230000037303 wrinkles Effects 0.000 claims description 10
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- 239000013543 active substance Substances 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000004576 sand Substances 0.000 abstract description 8
- 229920001153 Polydicyclopentadiene Polymers 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 4
- 230000002035 prolonged effect Effects 0.000 abstract description 4
- 238000011161 development Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 63
- 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 description 48
- 238000005452 bending Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000000465 moulding Methods 0.000 description 5
- 239000003822 epoxy resin Substances 0.000 description 4
- 229920000647 polyepoxide Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 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 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0812—Aluminium
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
Abstract
A high-temperature resistant die material of polydicyclopentadienyl and a preparation method thereof comprise a liquid A raw material and a liquid B raw material. The liquid A raw material components comprise, by weight, 25-85 parts of heat-conducting filler, 0.5-3 parts of surface modifier, and raw material DCPD: 15-74 parts; the raw material components of the liquid B comprise 40-400ppm Grubbs catalyst, 0.2-1.0 part of defoaming agent and 0.15-0.5 part of flatting agent according to parts by weight of DCPD monomer concentration in the liquid A. The invention adopts polydicyclopentadiene as the base material of the resin mould, the viscosity of the DCPD resin is low, so that sand holes and cavities caused by air bubbles in a system can be easily eliminated, the defects of difficult air bubble discharge and sand holes and cavities are eliminated, the heat-resistant temperature and the dimensional stability of the resin mould are improved, the service life of the resin mould under the high-temperature condition is prolonged, the forming period of the resin mould is shortened, and the development period and the cost of the mould are reduced.
Description
Technical Field
The invention relates to a high-temperature-resistant resin mold material, in particular to a polydicyclopentadienyl high-temperature-resistant mold material and a preparation method thereof.
Background
Compared with the traditional metal mold, the resin mold has the advantages of short manufacturing period, low cost and quick repair of damage, is particularly suitable for the industrial fields of products with complex shapes and quick replacement of products, and has wide application in the directions of plastic injection molds, blow molds, suction molds, foam forming molds and the like.
At present, the matrix materials of the resin mold mainly include silica gel and epoxy resin. The silica gel mould material is soft partially, and dimensional stability is worse under high temperature, leads to the deformation to appear easily in the forming process product. When the epoxy resin is used for manufacturing a resin mold, the viscosity is in the range of 1500-30000cps, bubbles generated by stirring in the molding process cannot be thoroughly removed, and the defects of cavities and sand holes exist on the surface and inside of the mold, so that the surface smoothness of the mold and the strength of the mold body are seriously influenced. The reaction is violent in heat release, gradual curing and post curing are needed, and a resin mold forming period needs 3-5 days and is long in duration. Meanwhile, due to poor heat resistance of the epoxy resin, the prepared resin mold is low in heat-resistant temperature, the problems of foaming, warping and scorching of the mold surface are easily caused in a high-temperature application scene, and the service life of the epoxy resin mold is shortened.
When dicyclopentadiene (DCPD) added with a traditional tungsten system as a catalyst is used as a component A and DCPD added with an accelerant aluminum alkyl is used as a component B, A, B components need to be mixed and poured under the protection of nitrogen for removing water and oxygen, the requirements on moisture and impurities in raw materials are extremely high, a large amount of heat conduction and enhanced filling cannot be carried out, and the DCPD cannot be applied to preparation of resin molds.
Disclosure of Invention
The invention aims to provide a high-temperature resistant die material of poly-dicyclopentadienyl and a preparation method thereof, which can eliminate the defects of difficult bubble discharge, sand holes and cavities, improve the heat-resistant temperature and the dimensional stability of a resin die, prolong the service life of the resin die under the high-temperature condition, shorten the molding cycle of the resin die, and reduce the development cycle and the cost of the die, so as to solve the problems in the background art.
In order to achieve the purpose, the invention provides the following technical scheme: a high-temperature resistant die material of poly-dicyclopentadienyl comprises a liquid A raw material and a liquid B raw material, wherein,
the liquid A raw material components comprise, by weight, 25-85 parts of heat-conducting filler, 0.5-3 parts of surface modifier and 15-74 parts of raw material DCPD;
the raw material components of the liquid B comprise 40-400ppm Grubbs catalyst, 0.2-1.0 part of defoaming agent and 0.15-0.5 part of flatting agent according to parts by weight of DCPD monomer concentration in the liquid A.
Further, the heat conducting filler is formed by mixing activated alumina and aluminum powder in a ratio of 1:1, the activated alumina is 3000 meshes, and the aluminum powder is 1200 meshes.
Further, the surface modifier is a low molecular weight active agent containing unsaturated bonds.
Further, the low molecular weight active agent is preferably one or more of hydroxypropyl acrylate, methacryloxypropyltrimethoxysilane (KH570), oleic acid and divinylbenzene.
Further, the defoaming agent and the leveling agent are combined into a processing aid.
The invention also provides a preparation method of the high-temperature-resistant die of the poly dicyclopentadienyl, which comprises the following steps:
s1: placing and fixing the 3D printed product model at the bottom of the mold frame;
s2: adding the measured heat-conducting filler and the surface modifier into a DCPD (Dicyclopentadiene) solution, intermittently stirring for 3h to enable the surface modifier and the heat-conducting filler to fully react, standing for later use after the reaction is finished, and marking as solution A;
s3: cutting the glass fiber felt cloth which is processed in advance into the shape of the surface of a mold, uniformly laying a layer on the upper surface of the fixed product 3D model, eliminating wrinkles as much as possible, and leaving a part of glass fiber felt cloth for later use;
s4: adding the measured Grubbs catalyst and the processing aid into the solution A, uniformly stirring and vacuumizing, and marking as solution B;
s5: pouring the solution B into a mold frame, laying the rest glass fiber felt cloth in the mold frame twice when the solution B is respectively poured with 1/4 and 1/2, and finally pouring the rest half of the solution B on the top;
s6: placing the mold in a vacuum box, vacuumizing for 10-30min, pushing the mold into a 90 ℃ oven, and curing for 30-120min to obtain a lower mold of the resin mold;
s7: and (3) reversing the cured lower die of the die by 180 degrees, building a die frame on the lower die, forming an upper die of the die by the same method, separating the cured upper die and the cured lower die, and taking out the 3D model of the product to obtain the resin die with the specific cavity.
Compared with the prior art, the invention has the beneficial effects that:
1. the DCPD resin adopted by the invention has low viscosity, so that sand holes and cavities caused by air bubbles in a system can be easily eliminated, the surface quality of the resin mould is improved, the resin mould can be reinforced by adopting glass fiber felt cloth due to the good infiltration of the low-viscosity resin, and the surface and the integral strength of the resin mould are greatly improved.
2. The thermal deformation temperature of the resin mould prepared by the invention is more than or equal to 150 ℃, the temporary use temperature upper limit can reach 200 ℃, the problem of warping and deformation of the resin mould under the high temperature condition is solved, and the service life is prolonged.
3. The invention has simple operation process, strong reflection controllability in the curing process, no central implosion and core burning phenomenon, maximum thickness of the integral casting molding can reach 450mm, and the molding period of the resin mold is short.
Detailed Description
The following examples will explain the present invention in detail, but the present invention is not limited thereto. 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.
Example 1
A high-temperature resistant die material of poly-dicyclopentadienyl and a preparation method thereof are disclosed, the material comprises a liquid A raw material and a liquid B raw material. The liquid A raw material components comprise 50 parts of heat-conducting filler, 1 part of hydroxypropyl acrylate, 0.3 part of divinylbenzene and 50 parts of raw material DCPD in parts by weight; the raw material component of the liquid B comprises a Grubbs catalyst which accounts for 200ppm of the concentration of the DCPD monomer in the liquid A, and the processing aid comprises 0.5 part of defoaming agent and 0.25 part of flatting agent. The invention comprises the following preparation steps:
step 1: placing and fixing the 3D printed product model at the bottom of the mold frame;
step 2: adding the measured heat-conducting filler and the surface modifier into a DCPD (Dicyclopentadiene) solution, intermittently stirring for 3h to enable the surface modifier and the heat-conducting filler to fully react, standing for later use after the reaction is finished, and marking as solution A;
and step 3: cutting the glass fiber felt cloth which is processed in advance into the shape of the surface of a mold, uniformly laying a layer on the upper surface of the fixed product 3D model, eliminating wrinkles as much as possible, and leaving a part of glass fiber felt cloth for later use;
and 4, step 4: adding the measured Grubbs catalyst and the processing aid into the solution A, uniformly stirring and vacuumizing, and marking as solution B;
and 5: pouring the solution B into a mold frame, laying the rest glass fiber felt cloth in the mold frame twice when the solution B is respectively poured with 1/4 and 1/2, and finally pouring the rest half of the solution B on the top;
step 6: placing the mold in a vacuum box, vacuumizing for 10min, pushing the mold into a 90 ℃ oven, and curing for 85min to obtain a lower mold of the resin mold;
and 7: and (3) reversing the cured lower die of the die by 180 degrees, building a die frame on the lower die, forming an upper die of the die by the same method, separating the cured upper die and the cured lower die, and taking out the 3D model of the product to obtain the resin die with the specific cavity.
Wherein the heat conducting filler is formed by mixing activated alumina and aluminum powder in a ratio of 1:1, the activated alumina is 3000 meshes, and the aluminum powder is 1200 meshes.
In this embodiment, the high temperature resistant mold of the prepared poly-dicyclopentadienyl has the following properties after testing: hardness 86 Shore D, compressive strength 80MPa, bending strength 160MPa, bending modulus 8.9GPa, and heat distortion temperature 150 ℃.
Example 2
A high-temperature resistant die material of poly-dicyclopentadienyl and a preparation method thereof are disclosed, the material comprises a liquid A raw material and a liquid B raw material. Wherein, the raw material components of the liquid A comprise 30 parts of heat-conducting filler, 2 parts of methacryloxypropyltrimethoxysilane (KH570) and 70 percent of DCPD; the raw material components of the liquid B comprise, by weight, Grubbs catalyst accounting for 350ppm of the concentration of the DCPD monomer in the liquid A, and the processing aid comprises 0.2 part of defoaming agent and 0.2 part of leveling agent.
The invention comprises the following preparation steps:
step 1: placing and fixing the 3D printed product model at the bottom of the mold frame;
step 2: adding the measured heat-conducting filler and the surface modifier into a DCPD (Dicyclopentadiene) solution, intermittently stirring for 3h to enable the surface modifier and the heat-conducting filler to fully react, standing for later use after the reaction is finished, and marking as solution A;
and step 3: cutting the glass fiber felt cloth which is processed in advance into the shape of the surface of a mold, uniformly laying a layer on the upper surface of the fixed product 3D model, eliminating wrinkles as much as possible, and leaving a part of glass fiber felt cloth for later use;
and 4, step 4: adding the measured Grubbs catalyst and the processing aid into the solution A, uniformly stirring and vacuumizing, and marking as solution B;
and 5: pouring the solution B into a mold frame, laying the rest glass fiber felt cloth in the mold frame twice when the solution B is respectively poured with 1/4 and 1/2, and finally pouring the rest half of the solution B on the top;
step 6: placing the mold in a vacuum box, vacuumizing for 15min, pushing the mold into a 90 ℃ oven, and curing for 80min to obtain a lower mold of the resin mold;
and 7: and (3) reversing the cured lower die of the die by 180 degrees, building a die frame on the lower die, forming an upper die of the die by the same method, separating the cured upper die and the cured lower die, and taking out the 3D model of the product to obtain the resin die with the specific cavity.
In this embodiment, the high temperature resistant mold of the prepared poly-dicyclopentadienyl has the following properties after testing: hardness of 84 Shore D, compressive strength of 75MPa, bending strength of 140MPa, bending modulus of 7.2GPa and heat distortion temperature of 155 ℃.
Example 3
The high-temperature resistant die material comprises a liquid A raw material and a liquid B raw material, wherein the liquid A raw material comprises 70 parts of heat-conducting filler, 2.5 parts of oleic acid, 0.1 part of divinylbenzene and 70 parts of raw material DCPD in parts by weight; the raw material components of the liquid B comprise, by weight, Grubbs catalyst accounting for 100ppm of the concentration of the DCPD monomer in the liquid A, and the processing aid comprises 0.85 part of defoaming agent and 0.5 part of leveling agent.
The invention comprises the following preparation steps:
step 1: placing and fixing the 3D printed product model at the bottom of the mold frame;
step 2: adding the measured heat-conducting filler and the surface modifier into a DCPD (Dicyclopentadiene) solution, intermittently stirring for 3h to enable the surface modifier and the heat-conducting filler to fully react, standing for later use after the reaction is finished, and marking as solution A;
and step 3: cutting the glass fiber felt cloth which is processed in advance into the shape of the surface of a mold, uniformly laying a layer on the upper surface of the fixed product 3D model, eliminating wrinkles as much as possible, and leaving a part of glass fiber felt cloth for later use;
and 4, step 4: adding the measured Grubbs catalyst and the processing aid into the solution A, uniformly stirring and vacuumizing, and marking as solution B;
and 5: pouring the solution B into a mold frame, laying the rest glass fiber felt cloth in the mold frame twice when the solution B is respectively poured with 1/4 and 1/2, and finally pouring the rest half of the solution B on the top;
step 6: placing the mold in a vacuum box, vacuumizing for 20min, pushing the mold into a 90 ℃ oven, and curing for 75min to obtain a lower mold of the resin mold;
and 7: and (3) reversing the cured lower die of the die by 180 degrees, building a die frame on the lower die, forming an upper die of the die by the same method, separating the cured upper die and the cured lower die, and taking out the 3D model of the product to obtain the resin die with the specific cavity.
In this embodiment, the high temperature resistant mold of the prepared poly-dicyclopentadienyl has the following properties after testing: hardness 91 Shore D, compressive strength 85MPa, bending strength 125MPa, bending modulus 9.3GPa, and heat distortion temperature 140 ℃.
Example 4
A polydicyclopentadiene-based high-temperature-resistant die material and a preparation method thereof are disclosed, the material comprises a liquid A raw material and a liquid B raw material, wherein the liquid A raw material comprises 25 parts by weight of heat-conducting filler, 1.5 parts by weight of methacryloxypropyltrimethoxysilane (KH570), 2% by weight of oleic acid and 74 parts by weight of DCPD (DCPD) serving as a raw material; the raw material components of the liquid B comprise 40ppm Grubbs catalyst accounting for the concentration of the DCPD monomer in the liquid A in parts by weight, and the processing aid comprises 0.6 part of defoaming agent and 0.4 part of leveling agent.
The invention comprises the following preparation steps:
step 1: placing and fixing the 3D printed product model at the bottom of the mold frame;
step 2: adding the measured heat-conducting filler and the surface modifier into a DCPD (Dicyclopentadiene) solution, intermittently stirring for 3h to enable the surface modifier and the heat-conducting filler to fully react, standing for later use after the reaction is finished, and marking as solution A;
and step 3: cutting the glass fiber felt cloth which is processed in advance into the shape of the surface of a mold, uniformly laying a layer on the upper surface of the fixed product 3D model, eliminating wrinkles as much as possible, and leaving a part of glass fiber felt cloth for later use;
and 4, step 4: adding the measured Grubbs catalyst and the processing aid into the solution A, uniformly stirring and vacuumizing, and marking as solution B;
and 5: pouring the solution B into a mold frame, laying the rest glass fiber felt cloth in the mold frame twice when the solution B is respectively poured with 1/4 and 1/2, and finally pouring the rest half of the solution B on the top;
step 6: placing the mold in a vacuum box, vacuumizing for 25min, pushing the mold into a 90 ℃ oven, and curing for 70min to obtain a lower mold of the resin mold;
and 7: and (3) reversing the cured lower die of the die by 180 degrees, building a die frame on the lower die, forming an upper die of the die by the same method, separating the cured upper die and the cured lower die, and taking out the 3D model of the product to obtain the resin die with the specific cavity.
In this embodiment, the high temperature resistant mold of the prepared poly-dicyclopentadienyl has the following properties after testing: hardness 88 Shore D, compression strength 80MPa, bending strength 130MPa, bending modulus 8.6GPa, and heat distortion temperature 150 ℃.
Example 5
A polydicyclopentadiene high temperature resistant mould material and a preparation method thereof, the material comprises a liquid A raw material and a liquid B raw material, wherein the liquid A raw material comprises 85 parts of heat conducting filler, 0.5 part of hydroxypropyl acrylate, 1.5 parts of methacryloxypropyl trimethoxysilane (KH570) and 15 parts of DCPD (dicumyl peroxide) serving as a raw material in parts by weight; the raw material components of the liquid B comprise, by weight, Grubbs catalyst accounting for 300ppm of the concentration of the DCPD monomer in the liquid A, and the processing aid comprises 0.3 part of defoaming agent and 0.3 part of leveling agent.
The invention comprises the following preparation steps:
step 1: placing and fixing the 3D printed product model at the bottom of the mold frame;
step 2: adding the measured heat-conducting filler and the surface modifier into a DCPD (Dicyclopentadiene) solution, intermittently stirring for 3h to enable the surface modifier and the heat-conducting filler to fully react, standing for later use after the reaction is finished, and marking as solution A;
and step 3: cutting the glass fiber felt cloth which is processed in advance into the shape of the surface of a mold, uniformly laying a layer on the upper surface of the fixed product 3D model, eliminating wrinkles as much as possible, and leaving a part of glass fiber felt cloth for later use;
and 4, step 4: adding the measured Grubbs catalyst and the processing aid into the solution A, uniformly stirring and vacuumizing, and marking as solution B;
and 5: pouring the solution B into a mold frame, laying the rest glass fiber felt cloth in the mold frame twice when the solution B is respectively poured with 1/4 and 1/2, and finally pouring the rest half of the solution B on the top;
step 6: placing the mold in a vacuum box, vacuumizing and discharging bubbles for 30min, pushing the mold into a 90 ℃ oven, and curing for 65min to obtain a lower mold of the resin mold;
and 7: and (3) reversing the cured lower die of the die by 180 degrees, building a die frame on the lower die, forming an upper die of the die by the same method, separating the cured upper die and the cured lower die, and taking out the 3D model of the product to obtain the resin die with the specific cavity.
In this embodiment, the high temperature resistant mold of the prepared poly-dicyclopentadienyl has the following properties after testing: hardness 90 Shore D, compressive strength 78MPa, bending strength 135MPa, bending modulus 7.5GPa, and heat distortion temperature 145 ℃.
Example 6
A high-temperature resistant die material of poly-dicyclopentadienyl and a preparation method thereof are disclosed, the material comprises a liquid A raw material and a liquid B raw material. Wherein, the raw material components of the liquid A comprise 60 parts of heat-conducting filler, 0.6 part of hydroxypropyl acrylate, 0.8 part of divinylbenzene and 40 parts of raw material DCPD in parts by weight; the raw material components of the liquid B comprise, by weight, Grubbs catalyst accounting for 400ppm of the concentration of the DCPD monomer in the liquid A, and the processing aid comprises 1 part of defoaming agent and 0.15 part of leveling agent.
The invention comprises the following preparation steps:
step 1: placing and fixing the 3D printed product model at the bottom of the mold frame;
step 2: adding the measured heat-conducting filler and the surface modifier into a DCPD (Dicyclopentadiene) solution, intermittently stirring for 3h to enable the surface modifier and the heat-conducting filler to fully react, standing for later use after the reaction is finished, and marking as solution A;
and step 3: cutting the glass fiber felt cloth which is processed in advance into the shape of the surface of a mold, uniformly laying a layer on the upper surface of the fixed product 3D model, eliminating wrinkles as much as possible, and leaving a part of glass fiber felt cloth for later use;
and 4, step 4: adding the measured Grubbs catalyst and the processing aid into the solution A, uniformly stirring and vacuumizing, and marking as solution B;
and 5: pouring the solution B into a mold frame, laying the rest glass fiber felt cloth in the mold frame twice when the solution B is respectively poured with 1/4 and 1/2, and finally pouring the rest half of the solution B on the top;
step 6: placing the mold in a vacuum box, vacuumizing for 10min, pushing the mold into a 90 ℃ oven, and curing for 120min to obtain a lower mold of the resin mold;
and 7: and (3) reversing the cured lower die of the die by 180 degrees, building a die frame on the lower die, forming an upper die of the die by the same method, separating the cured upper die and the cured lower die, and taking out the 3D model of the product to obtain the resin die with the specific cavity.
In this embodiment, the high temperature resistant mold of the prepared poly-dicyclopentadienyl has the following properties after testing: hardness 85 Shore D, compressive strength 85MPa, bending strength 140MPa, bending modulus 9.0GPa, and heat distortion temperature 130 ℃.
Example 7
A high-temperature resistant die material of poly-dicyclopentadienyl and a preparation method thereof are disclosed, the material comprises a liquid A raw material and a liquid B raw material. Wherein, the raw material components of the liquid A comprise 55 parts of heat-conducting filler, 0.4 part of methacryloxypropyltrimethoxysilane (KH570), 0.6 part of divinylbenzene and 45 parts of DCPD; the raw material components of the liquid B comprise, by weight, Grubbs catalyst accounting for 250ppm of the concentration of the DCPD monomer in the liquid A, and the processing aid comprises 0.8 part of defoaming agent and 0.4 part of leveling agent.
The invention comprises the following preparation steps:
step 1: placing and fixing the 3D printed product model at the bottom of the mold frame;
step 2: adding the measured heat-conducting filler and the surface modifier into a DCPD (Dicyclopentadiene) solution, intermittently stirring for 3h to enable the surface modifier and the heat-conducting filler to fully react, standing for later use after the reaction is finished, and marking as solution A;
and step 3: cutting the glass fiber felt cloth which is processed in advance into the shape of the surface of a mold, uniformly laying a layer on the upper surface of the fixed product 3D model, eliminating wrinkles as much as possible, and leaving a part of glass fiber felt cloth for later use;
and 4, step 4: adding the measured Grubbs catalyst and the processing aid into the solution A, uniformly stirring and vacuumizing, and marking as solution B;
and 5: pouring the solution B into a mold frame, laying the rest glass fiber felt cloth in the mold frame twice when the solution B is respectively poured with 1/4 and 1/2, and finally pouring the rest half of the solution B on the top;
step 6: placing the mold in a vacuum box, vacuumizing for 15min, pushing the mold into a 90 ℃ oven, and curing for 100min to obtain a lower mold of the resin mold;
and 7: and (3) reversing the cured lower die of the die by 180 degrees, building a die frame on the lower die, forming an upper die of the die by the same method, separating the cured upper die and the cured lower die, and taking out the 3D model of the product to obtain the resin die with the specific cavity.
In this embodiment, the high temperature resistant mold of the prepared poly-dicyclopentadienyl has the following properties after testing: hardness 93 Shore D, compressive strength 82MPa, bending strength 135MPa, bending modulus 7.8GPa, and heat distortion temperature 145 ℃.
Example 8
A high-temperature resistant die material of poly-dicyclopentadienyl and a preparation method thereof are disclosed, the material comprises a liquid A raw material and a liquid B raw material. Wherein, the raw material components of the liquid A comprise 40 parts of heat-conducting filler, 0.6 part of divinyl benzene and 60 parts of raw material DCPD in parts by weight; the raw material components of the liquid B comprise, by weight, Grubbs catalyst which accounts for 150ppm of the concentration of the DCPD monomer in the liquid A, and the processing aid comprises 0.7 part of defoaming agent and 0.3 part of leveling agent.
The invention comprises the following preparation steps:
step 1: placing and fixing the 3D printed product model at the bottom of the mold frame;
step 2: adding the measured heat-conducting filler and the surface modifier into a DCPD (Dicyclopentadiene) solution, intermittently stirring for 3h to enable the surface modifier and the heat-conducting filler to fully react, standing for later use after the reaction is finished, and marking as solution A;
and step 3: cutting the glass fiber felt cloth which is processed in advance into the shape of the surface of a mold, uniformly laying a layer on the upper surface of the fixed product 3D model, eliminating wrinkles as much as possible, and leaving a part of glass fiber felt cloth for later use;
and 4, step 4: adding the measured Grubbs catalyst and the processing aid into the solution A, uniformly stirring and vacuumizing, and marking as solution B;
and 5: pouring the solution B into a mold frame, laying the rest glass fiber felt cloth in the mold frame twice when the solution B is respectively poured with 1/4 and 1/2, and finally pouring the rest half of the solution B on the top;
step 6: placing the mold in a vacuum box, vacuumizing and removing bubbles for 20min, pushing the mold into a 90 ℃ oven, and curing for 90min to obtain a lower mold of the resin mold;
and 7: and (3) reversing the cured lower die of the die by 180 degrees, building a die frame on the lower die, forming an upper die of the die by the same method, separating the cured upper die and the cured lower die, and taking out the 3D model of the product to obtain the resin die with the specific cavity.
In this embodiment, the high temperature resistant mold of the prepared poly-dicyclopentadienyl has the following properties after testing: hardness of 88 Shore D, compressive strength of 82MPa, bending strength of 140MPa, bending modulus of 8.8GPa and heat deformation temperature of 150 ℃.
The above section shows 8 examples, and the following shows 1 comparative example:
comparative example: the liquid A comprises the following raw material components: 50% of heat-conducting filler and 50% of raw material DCPD, wherein the raw material component of the liquid B comprises a Grubbs catalyst which accounts for 200ppm of the concentration of the DCPD monomer in the liquid A, and the processing aid comprises: 0.5 percent of defoaming agent and 0.25 percent of flatting agent. The preparation method is the same as that of the embodiment 1 of the invention, and the prepared die is tested to have the following properties: hardness of 75 Shore D, compressive strength of 56MPa, bending strength of 90MPa, bending modulus of 5.6GPa and heat distortion temperature of 105 ℃.
The material formulations of the 8 examples of the invention and of the comparative examples are compiled in table 1:
table 1 comparison of material formulations of examples and comparative examples
The resin mold properties of 8 examples of the present invention and the comparative examples are summarized in Table 2:
TABLE 2 comparison of die Properties of examples and comparative examples
As can be seen from the above 8 examples and comparative examples, because the comparative example does not use a surface modifier, compared with the comparative example, the performance parameters (hardness, compressive strength, bending modulus and thermal deformation temperature) of the mold of the invention are obviously superior to those of the mold of the comparative example, the polydicyclopentadiene is used as a resin mold base material, the viscosity of the DCPD resin is low, sand holes and cavities caused by air bubbles in a system are easily eliminated, the surface quality of the resin mold is improved, the resin mold can be reinforced by adopting glass fiber felt cloth due to good infiltration of low-viscosity resin, the surface and the overall strength of the resin mold are greatly improved, the thermal deformation temperature of the prepared resin mold is not less than 150 ℃, the upper limit of the temporary use temperature can reach 200 ℃, and the problem of warping deformation of the resin mold under the high temperature condition is improved, the service life is prolonged.
In summary, the following steps: according to the high-temperature-resistant die material of the poly-dicyclopentadiene and the preparation method thereof, the poly-dicyclopentadiene is used as a resin die base material, the DCPD resin has low viscosity, so that sand holes and cavities caused by air bubbles in a system are easily eliminated, the defects of difficult air bubble discharge and sand holes and cavities are eliminated, the heat-resistant temperature and the size stability of the resin die are improved, the service life of the resin die under a high-temperature condition is prolonged, the molding cycle of the resin die is shortened, and the development cycle and the cost of the die are reduced.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (2)
1. A high-temperature resistant die material of poly-dicyclopentadienyl is characterized by comprising a liquid A raw material and a liquid B raw material, wherein,
the liquid A raw material components comprise, by weight, 25-85 parts of heat-conducting filler, 0.5-3 parts of surface modifier and 15-74 parts of raw material DCPD;
the raw material components of the liquid B comprise 40-400ppm of Grubbs catalyst, 0.2-1.0 part of defoaming agent and 0.15-0.5 part of flatting agent in parts by weight, wherein the Grubbs catalyst accounts for the concentration of DCPD monomers in the liquid A;
the heat-conducting filler is prepared by mixing 1:1 active alumina and aluminum powder, wherein the active alumina is 3000 meshes, and the aluminum powder is 1200 meshes;
the surface modifier is a low molecular weight active agent containing unsaturated bonds;
the low molecular weight active agent is one or more of hydroxypropyl acrylate, methacryloxypropyl trimethoxy silane KH570, oleic acid and divinylbenzene;
and the defoaming agent and the flatting agent are combined into a processing aid.
2. A method for preparing a high temperature resistant mold using the high temperature resistant mold material of polydicyclopentadienyl according to claim 1, comprising the steps of:
s1: placing and fixing the 3D printed product model at the bottom of the mold frame;
s2: adding the measured heat-conducting filler and the measured surface modifier into the DCPD solution, intermittently stirring for 3 hours to ensure that the surface modifier and the heat-conducting filler are fully reacted, standing for later use after the reaction is finished, and marking as solution A;
s3: cutting the glass fiber felt cloth which is processed in advance into the shape of the surface of a mold, uniformly laying a layer on the upper surface of the fixed product 3D model, eliminating wrinkles as much as possible, and leaving a part of glass fiber felt cloth for later use;
s4: adding the measured Grubbs catalyst and the processing aid into the solution A, uniformly stirring and vacuumizing, and marking as solution B;
s5: pouring the solution B into a mold frame, laying the rest glass fiber felt cloth in the mold frame twice when the solution B is respectively poured with 1/4 and 1/2, and finally pouring the rest half of the solution B on the top;
s6: placing the mold in a vacuum box, vacuumizing for 10-30min, pushing the mold into a 90 ℃ oven, and curing for 30-120min to obtain a lower mold of the resin mold;
s7: and (3) reversing the cured lower die of the die by 180 degrees, building a die frame on the lower die, forming an upper die of the die by the same method, separating the cured upper die and the cured lower die, and taking out the 3D model of the product to obtain the resin die with the specific cavity.
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| GB9927431D0 (en) * | 1999-11-22 | 2000-01-19 | Ciba Sc Holding Ag | Casting resin and process for the fabrication of resin molds |
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Denomination of invention: A high-temperature resistant mold material based on polydicyclopentadiene and its preparation method Effective date of registration: 20231127 Granted publication date: 20220422 Pledgee: Guangdong Qingxin Rural Commercial Bank Co.,Ltd. Taiping Branch Pledgor: GUANGDONG JUHANG INSTITUTE FOR ADVANCED MATERIALS Co.,Ltd. Registration number: Y2023980067643 |
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