CN117777420A - Heat-resistant unsaturated polyester resin and preparation method thereof - Google Patents
Heat-resistant unsaturated polyester resin and preparation method thereof Download PDFInfo
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- CN117777420A CN117777420A CN202311840250.1A CN202311840250A CN117777420A CN 117777420 A CN117777420 A CN 117777420A CN 202311840250 A CN202311840250 A CN 202311840250A CN 117777420 A CN117777420 A CN 117777420A
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- unsaturated polyester
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- 229920006337 unsaturated polyester resin Polymers 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 8
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 24
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims abstract description 24
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 22
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 19
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000003112 inhibitor Substances 0.000 claims abstract description 12
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 11
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 11
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 claims abstract description 8
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 8
- 239000010941 cobalt Substances 0.000 claims abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004611 light stabiliser Substances 0.000 claims abstract description 8
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims description 109
- 238000006243 chemical reaction Methods 0.000 claims description 63
- 238000010438 heat treatment Methods 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 18
- 230000001276 controlling effect Effects 0.000 claims description 17
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000007789 sealing Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000011261 inert gas Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000002347 injection Methods 0.000 claims description 7
- 239000007924 injection Substances 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- WSXIMVDZMNWNRF-UHFFFAOYSA-N antimony;ethane-1,2-diol Chemical compound [Sb].OCCO WSXIMVDZMNWNRF-UHFFFAOYSA-N 0.000 claims description 4
- PWEVMPIIOJUPRI-UHFFFAOYSA-N dimethyltin Chemical compound C[Sn]C PWEVMPIIOJUPRI-UHFFFAOYSA-N 0.000 claims description 4
- 230000005389 magnetism Effects 0.000 claims description 4
- CRHIAMBJMSSNNM-UHFFFAOYSA-N tetraphenylstannane Chemical compound C1=CC=CC=C1[Sn](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CRHIAMBJMSSNNM-UHFFFAOYSA-N 0.000 claims description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 3
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 239000003063 flame retardant Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 12
- 230000006872 improvement Effects 0.000 description 4
- 230000013011 mating Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 230000006978 adaptation Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Polyesters Or Polycarbonates (AREA)
Abstract
The application discloses heat-resistant unsaturated polyester resin and a preparation method thereof, and relates to the technical field of unsaturated polyester resin, wherein the heat-resistant unsaturated polyester resin comprises the following components in parts by weight: 42 to 47 parts by weight of phthalic anhydride, 8 to 11 parts by weight of maleic anhydride, 23 to 35 parts by weight of isophthalic acid, 57 to 62 parts by weight of diethylene glycol, 15 to 25 parts by weight of propylene glycol, 3.8 to 4.7 parts by weight of a catalyst, 1.5 to 4 parts by weight of benzoic acid, 19 to 22 parts by weight of fumaric anhydride, 0.7 to 1.2 parts by weight of a polymerization inhibitor, 1.1 to 2.6 parts by weight of triphenyl phosphate, 0.3 to 0.7 part by weight of a promoter cobalt iso-octoate, 1.1 to 1.5 parts by weight of an antioxidant, 0.4 to 0.6 part by weight of a light stabilizer and 2.5 to 3.8 parts by weight of a curing agent methyl ethyl ketone peroxide; the heat resistance, the flame resistance and the dimensional stability of the unsaturated polyester resin can be improved, so that the unsaturated polyester resin can meet the technical effect of certain use requirements.
Description
Technical Field
The invention relates to the technical field of unsaturated polyester resin, in particular to heat-resistant unsaturated polyester resin and a preparation method thereof.
Background
The unsaturated polyester resin is generally a linear polymer compound having an ester bond and an unsaturated double bond, which is obtained by polycondensation of an unsaturated dibasic acid diol or a saturated dibasic acid unsaturated diol. In general, the polyesterification polycondensation is carried out at 190 to 220℃until the desired acid value (or viscosity) is reached, after the end of the polyesterification polycondensation, a certain amount of vinyl monomer is added while hot to prepare a viscous liquid, such polymer solution being known as an unsaturated polyester resin, which is an important thermosetting resin species developed in the plastics industry.
Unsaturated polyester resin plays a main role in parts of automobiles, electric appliances and electronic products, and with the continuous improvement of the living standard of people, the requirements for the automobiles, the electric appliances and the electronic products are increasingly increased, and in the use and processing process, higher requirements are put on the heat resistance, the flame resistance and the dimensional stability of the unsaturated polyester material; therefore, improvement of heat resistance of unsaturated polyester resins has become a great trend of development of properties thereof in the future.
Disclosure of Invention
The application solves the technical problem that the heat resistance, the flame resistance and the dimensional stability of the unsaturated polyester resin in the prior art cannot completely meet the use requirement by providing the heat-resistant unsaturated polyester resin and the preparation method thereof; the heat resistance, the flame resistance and the dimensional stability of the unsaturated polyester resin are improved, so that the unsaturated polyester resin can meet the technical effect of certain use requirements.
The application provides a heat-resistant unsaturated polyester resin, which comprises the following components in parts by weight:
42 to 47 parts by weight of phthalic anhydride, 8 to 11 parts by weight of maleic anhydride, 23 to 35 parts by weight of isophthalic acid, 57 to 62 parts by weight of diethylene glycol, 15 to 25 parts by weight of propylene glycol, 3.8 to 4.7 parts by weight of a catalyst, 1.5 to 4 parts by weight of benzoic acid, 19 to 22 parts by weight of fumaric anhydride, 0.7 to 1.2 parts by weight of a polymerization inhibitor, 1.1 to 2.6 parts by weight of triphenyl phosphate, 0.3 to 0.7 part by weight of a promoter cobalt iso-octoate, 1.1 to 1.5 parts by weight of an antioxidant, 0.4 to 0.6 part by weight of a light stabilizer and 2.5 to 3.8 parts by weight of a curing agent methyl ethyl ketone peroxide;
wherein the catalyst is prepared by mixing ethylene glycol antimony, dimethyl tin and tetraphenyl tin according to a molar ratio of 1:1:4; the polymerization inhibitor is prepared by mixing hydroquinone, hydroquinone and p-benzoquinone according to the weight ratio of 6:1:2.
A method for preparing heat-resistant unsaturated polyester resin, comprising:
s100: premixing, namely adding phthalic anhydride, maleic anhydride, isophthalic acid, diethylene glycol, propylene glycol and a catalyst into a reactor, starting stirring and slowly heating to 330-410 ℃, and carrying out heat preservation reaction for 50-90 minutes;
s200: after the reaction is finished, the temperature is reduced to 80 to 120 ℃ and benzoic acid and fumaric acid anhydride are added, inert gas is introduced, stirring is started, the temperature is increased to 220 to 260 ℃ for polymerization, and the polymerization time is 45 to 50 minutes;
s300: after the secondary mixing, closing an inert gas valve, reducing the temperature to 75-90 ℃, adding a polymerization inhibitor and a stabilizer, heating to 130-180 ℃ and stirring for 60-90 minutes;
s400: mixing for three times, adding the accelerator cobalt iso-octoate, stirring and heating to 130-150 ℃, wherein the stirring time is 45-70 minutes, adding the antioxidant II and the light stabilizer, stirring again for 60-90 minutes, and taking out after stirring is completed;
s500: baking, namely placing the obtained material into a baking oven for baking for 30-45 minutes, setting the temperature of the baking oven to be 90-105 ℃, taking out the baked material and placing the baked material into a clean reactor;
s600: mixing four times, adding the curing agent methyl ethyl ketone peroxide, and starting stirring, wherein the stirring temperature is 30-45 ℃, and the stirring time is 45-70 minutes;
s700: and (3) curing, namely placing the mixture into a curing furnace for curing after stirring, wherein the curing temperature is 85-95 ℃ and the curing time is 9-12 hours, and thus obtaining the heat-resistant flame-retardant unsaturated polyester resin.
Further, the reactor comprises a reaction box body, a heating shell and a stirring device; the whole reaction box body is a hollow cylinder arranged vertically, the whole heating shell is a round tube arranged vertically, and the heating shell is sleeved on the reaction box body; the heating shell has the functions of temperature detection, temperature setting and timing reminding; the top end of the reaction box body is provided with a sealing cover for placing materials and an air injection pipe for injecting inert gas, the top of the side wall of the reaction box body is provided with a suction pipe for exhausting air, and the bottom of the side wall of the reaction box body is provided with a discharge pipe; the stirring device comprises a driving motor, a stirring shaft and a plurality of stirring blades, wherein the driving motor is fixed at the top of the reaction box body, and the positions of the sealing cover and the suction pipe are staggered with the driving motor; the motor shaft of the driving motor penetrates through the shell of the reaction box body and stretches into the reaction box body, and the motor shaft of the driving motor is fixedly connected with the stirring shaft; the stirring shaft and the motor shaft of the driving motor are vertically arranged, a plurality of stirring blades are uniformly fixed on the stirring shaft, and the whole stirring blades are horizontally arranged cylinders; the length of the stirring blade is not less than two thirds of the inner radius of the reaction box body.
Further, step S200 includes:
s210: placing materials, cooling to 80-120 ℃, opening a sealing cover, and placing benzoic acid and fumaric anhydride into a reaction box;
s220: the inert atmosphere controls the suction pipe to suck air, and simultaneously, the inert gas is continuously injected into the reaction box body through the gas injection pipe;
s230: stirring reaction, controlling the heating shell to be heated to 220-260 ℃, and then starting the driving motor to enable the stirring shaft to drive the stirring blade to stir, and setting the time to be 45-50 minutes.
Further, the stirring blade comprises a shell, an adjusting cavity, an inner blade, a clamping block and an inner spring; the whole shell is a cylinder which is horizontally arranged, and the shell is fixed on the stirring shaft; a plurality of adjusting cavities are uniformly formed in the shell along the length direction, and the top end and the bottom end of each adjusting cavity are provided with identical rectangular openings; two inner blades are arranged in each adjusting cavity, and the inner blades correspond to the clamping blocks one by one; the two inner blades are respectively and slidably connected in the upper end opening and the lower end opening of the adjusting cavity, and high-temperature-resistant sealing rings for sealing are arranged between the upper end opening and the lower end opening of the adjusting cavity and the outer wall of the inner blade; two opposite surfaces of the inner blades in the same adjusting cavity are respectively fixed with a limiting clamping block, and the width of each clamping block is larger than that of an opening at the upper end of the adjusting cavity; at least two internal compression springs are fixed between two clamping blocks in the same adjusting cavity; and when the linear distance between the two corresponding clamping blocks is maximum, the internal pressure spring is in a normal state.
Further, an inner magnetic part is fixed in the middle position inside the adjusting cavity, and the whole inner magnetic part is a cuboid which is horizontally arranged; the inner magnetic piece is a direct current electromagnet, and magnetic poles of the inner magnetic piece are positioned at the upper end and the lower end; the clamping blocks are permanent magnets, and the magnetic poles of opposite faces of the two clamping blocks in the same adjusting cavity are the same.
Further, step S230 includes:
s231: heating, namely controlling the heating shell to be heated to 220-260 ℃;
s232: adjusting, starting the inner magnetic part, enabling the inner magnetic part and the clamping block to mutually magnetically attract, further controlling the inner blade to be in a retracted state, and then starting the driving motor, wherein the setting time is 45-50 minutes;
s233: the automatic adjustment is carried out, as the temperature in the mixture rises, the magnetism of the inner magnetic piece and the clamping block is weakened, so that the magnetic attraction between the inner magnetic piece and the clamping block is reduced, and the inner blade gradually extends out of the shell, so that the stirring efficiency is improved;
s234: and actively adjusting the magnetic size of the inner magnetic piece to actively control the extension degree of the inner blade.
Further, the housing includes a plurality of rotating units and a plurality of rotating parts; the rotating units and the adjusting cavities are the same in number and correspond to each other one by one, the rotating units are hollow cylinders as a whole, the adjusting cavities are internal spaces of the corresponding rotating units, and the inner blades are connected to the corresponding rotating units in a sliding manner; and a rotating part is rotationally connected between two adjacent rotating units, and one rotating unit on the shell, which is close to the stirring shaft, is fixed on the stirring shaft.
Further, two arc-shaped nets are symmetrically fixed between two inner blades on the same rotating unit, and the arc-shaped nets are made of stainless steel nets; the two arc-shaped nets are positioned at the outer sides of the corresponding rotating units, and the concave surfaces of the arc-shaped nets face the corresponding rotating units.
Further, step S230 includes:
s231: heating, namely controlling the heating shell to be heated to 220-260 ℃;
s232: adjusting, starting the inner magnetic part, enabling the inner magnetic part and the clamping block to mutually magnetically attract, further controlling the inner blade to be in a retracted state, and then starting the driving motor, wherein the setting time is 45-50 minutes;
s233: vibration stirring, the magnetic size of the inner magnetic part is continuously changed through the control of the control unit, so that the extension length of the inner blade is continuously changed, and the arc-shaped net is driven to vibrate and stir the mixture inside the reaction box body, so that stirring efficiency is improved.
One or more technical solutions provided in the present application have at least the following technical effects or advantages:
by providing a heat-resistant unsaturated polyester resin, the heat-resistant unsaturated polyester resin comprises the following components in parts by weight: 42 to 47 parts by weight of phthalic anhydride, 8 to 11 parts by weight of maleic anhydride, 23 to 35 parts by weight of isophthalic acid, 57 to 62 parts by weight of diethylene glycol, 15 to 25 parts by weight of propylene glycol, 3.8 to 4.7 parts by weight of a catalyst, 1.5 to 4 parts by weight of benzoic acid, 19 to 22 parts by weight of fumaric anhydride, 0.7 to 1.2 parts by weight of a polymerization inhibitor, 1.1 to 2.6 parts by weight of triphenyl phosphate, 0.3 to 0.7 part by weight of a promoter cobalt iso-octoate, 1.1 to 1.5 parts by weight of an antioxidant, 0.4 to 0.6 part by weight of a light stabilizer and 2.5 to 3.8 parts by weight of a curing agent methyl ethyl ketone peroxide; wherein the catalyst is prepared by mixing ethylene glycol antimony, dimethyl tin and tetraphenyl tin according to a molar ratio of 1:1:4; the polymerization inhibitor is prepared by mixing hydroquinone, hydroquinone and p-benzoquinone according to the weight ratio of 6:1:2; the technical problem that the heat resistance, the flame resistance and the dimensional stability of unsaturated polyester resin in the prior art cannot completely meet the use requirements is effectively solved; further, the heat resistance, the flame resistance and the dimensional stability of the unsaturated polyester resin are improved, so that the unsaturated polyester resin can meet the technical effect of certain use requirements.
Drawings
FIG. 1 is a schematic flow chart of a process for preparing a heat-resistant unsaturated polyester resin according to the invention;
FIG. 2 is a schematic structural view of a reactor set for the method for producing heat-resistant unsaturated polyester resin according to the invention;
FIG. 3 is a schematic flow chart of the polymerization reaction of FIG. 1 according to the present invention;
FIG. 4 is a schematic view of the stirring blade of a mating reactor of the method for preparing heat-resistant unsaturated polyester resin according to the invention;
FIG. 5 is a schematic view showing the structure of stirring blades of a matching reactor in the method for preparing heat-resistant unsaturated polyester resin according to the invention;
FIG. 6 is a schematic diagram showing the locations of the clamping blocks of the matching reactor in the preparation method of the heat-resistant unsaturated polyester resin according to the invention;
FIG. 7 is a schematic view of the position of the inner magnetic member of the reactor of the process for producing heat-resistant unsaturated polyester resin according to the invention;
FIG. 8 is a schematic view showing a packed state of inner blades of a supporting reactor of the method for producing a heat-resistant unsaturated polyester resin according to the invention;
FIG. 9 is a schematic illustration of a flow scheme for the agitation of FIG. 3 in accordance with the present invention;
FIG. 10 is a schematic diagram showing the structure of a shell of a reactor used in the method for producing heat-resistant unsaturated polyester resin according to the invention;
FIG. 11 is a schematic view of the arcuate screen position of a mating reactor of the process for preparing a heat resistant unsaturated polyester resin of the invention;
FIG. 12 is a schematic side view of an arcuate screen with the inner blades of a mating reactor of the method of preparing a heat resistant unsaturated polyester resin of the invention extended;
FIG. 13 is a schematic side view of an arcuate web with the inner blades of a mating reactor of the method of making a heat resistant unsaturated polyester resin of the invention stowed;
FIG. 14 is a schematic illustration of another flow scheme for the agitation of FIG. 3 in accordance with the present invention.
In the figure:
the reaction box 100, the sealing cover 110, the suction pipe 120, the gas injection pipe 130, the discharge pipe 140, the heating shell 200, the driving motor 300, the stirring shaft 400, the stirring blade 500, the outer shell 510, the rotating unit 511, the rotating part 512, the adjusting cavity 520, the inner blade 530, the clamping block 540, the inner spring 550, the inner magnetic piece 560 and the arc-shaped net 570.
Detailed Description
In order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended drawings; the preferred embodiments of the present invention are illustrated in the drawings, however, the present invention may be embodied in many different forms and is not limited to the embodiments described herein; rather, these embodiments are provided so that this disclosure will be thorough and complete.
It should be noted that the terms "vertical", "horizontal", "upper", "lower", "left", "right", and the like are used herein for illustrative purposes only and do not represent the only embodiment.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs; the terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention; the term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Example 1
The heat-resistant unsaturated polyester resin comprises the following components in parts by weight:
42 to 47 parts by weight of phthalic anhydride, 8 to 11 parts by weight of maleic anhydride, 23 to 35 parts by weight of isophthalic acid, 57 to 62 parts by weight of diethylene glycol, 15 to 25 parts by weight of propylene glycol, 3.8 to 4.7 parts by weight of a catalyst, 1.5 to 4 parts by weight of benzoic acid, 19 to 22 parts by weight of fumaric anhydride, 0.7 to 1.2 parts by weight of a polymerization inhibitor, 1.1 to 2.6 parts by weight of triphenyl phosphate, 0.3 to 0.7 part by weight of a promoter cobalt iso-octoate, 1.1 to 1.5 parts by weight of an antioxidant, 0.4 to 0.6 part by weight of a light stabilizer and 2.5 to 3.8 parts by weight of a curing agent methyl ethyl ketone peroxide;
wherein the catalyst is prepared by mixing ethylene glycol antimony, dimethyl tin and tetraphenyl tin according to a molar ratio of 1:1:4; the polymerization inhibitor is prepared by mixing hydroquinone, hydroquinone and p-benzoquinone according to the weight ratio of 6:1:2.
As shown in fig. 1, the preparation method of the heat-resistant unsaturated polyester resin comprises the following steps:
s100: premixing, namely adding phthalic anhydride, maleic anhydride, isophthalic acid, diethylene glycol, propylene glycol and a catalyst into a reactor, starting stirring and slowly heating to 330-410 ℃, and carrying out heat preservation reaction for 50-90 minutes;
s200: after the reaction is finished, the temperature is reduced to 80 to 120 ℃ and benzoic acid and fumaric acid anhydride are added, inert gas is introduced, stirring is started, the temperature is increased to 220 to 260 ℃ for polymerization, and the polymerization time is 45 to 50 minutes;
s300: after the secondary mixing, closing an inert gas valve, reducing the temperature to 75-90 ℃, adding a polymerization inhibitor and a stabilizer, heating to 130-180 ℃ and stirring for 60-90 minutes;
s400: mixing for three times, adding the accelerator cobalt iso-octoate, stirring and heating to 130-150 ℃, wherein the stirring time is 45-70 minutes, adding the antioxidant II and the light stabilizer, stirring again for 60-90 minutes, and taking out after stirring is completed;
s500: baking, namely placing the obtained material into a baking oven for baking for 30-45 minutes, setting the temperature of the baking oven to be 90-105 ℃, taking out the baked material and placing the baked material into a clean reactor;
s600: mixing four times, adding the curing agent methyl ethyl ketone peroxide, and starting stirring, wherein the stirring temperature is 30-45 ℃, and the stirring time is 45-70 minutes;
s700: and (3) curing, namely placing the mixture into a curing furnace for curing after stirring, wherein the curing temperature is 85-95 ℃ and the curing time is 9-12 hours, and thus obtaining the heat-resistant flame-retardant unsaturated polyester resin.
Preferably, the temperature rising rate in step S100 is 2 to 7 degrees celsius per minute; the temperature rising rate in the step S200 is 13-18 ℃ per minute; the temperature rising rate in step S300 and step S400 is 10-15 ℃ per minute.
The technical scheme in the embodiment of the application at least has the following technical effects or advantages:
the heat resistance, the flame resistance and the dimensional stability of the unsaturated polyester resin are improved, so that the unsaturated polyester resin can meet the technical effect of certain use requirements.
Example two
In the embodiment, when the existing reactor is used for reaction, parameters such as temperature, pressure and the like in the reaction process cannot be monitored in real time; the embodiment of the application is optimized to a certain extent on the basis of the embodiment.
As shown in fig. 2, the reactor includes a reaction tank 100, a heating case 200, a stirring device, a power assembly, and a control unit; the whole reaction box body 100 is a hollow cylinder arranged vertically, the whole heating shell 200 is a round tube arranged vertically, and the heating shell 200 is sleeved on the reaction box body 100; the heating shell 200 has the functions of temperature detection, temperature setting and timing reminding; the top end of the reaction box body 100 is provided with a sealing cover 110 for placing materials and an air injection pipe 130 for injecting inert gas, the top of the side wall of the reaction box body 100 is provided with a suction pipe 120 for exhausting air, and the bottom of the side wall of the reaction box body 100 is provided with a discharge pipe 140; the stirring device comprises a driving motor 300, a stirring shaft 400 and a plurality of stirring blades 500, wherein the driving motor 300 is fixed at the top of the reaction box body 100, and the positions of the sealing cover 110 and the suction pipe 120 are staggered with the driving motor 300; a motor shaft of the driving motor 300 penetrates through the shell of the reaction box body 100 and stretches into the reaction box body 100, and the motor shaft of the driving motor 300 is fixedly connected with the stirring shaft 400; the motor shafts of the stirring shaft 400 and the driving motor 300 are vertically arranged, a plurality of stirring blades 500 are uniformly fixed on the stirring shaft 400, and the whole stirring blades 500 are horizontally arranged cylinders; the length of the stirring vane 500 is not less than two thirds of the inner radius of the reaction chamber 100.
Preferably, the number of the stirring blades 500 is 8 to 16.
Preferably, a gas flowmeter and a gas concentration meter are installed on the inner wall of the top end of the reaction box 100, and a barometer is installed on the outer wall of the top end of the reaction box 100, for measuring the gas pressure value inside the reaction box 100.
The power assembly is used for supplying power for the operation of the reactor, and is preferably an alternating current power supply or a battery; the control unit is used for controlling the coordinated operation of all parts of the reactor, and is preferably a programmable logic controller; all are prior art and are not described in detail herein.
As shown in fig. 3, the step S200 includes:
s210: placing materials, cooling to 80-120 ℃, opening a sealing cover 110 and placing benzoic acid and fumaric acid anhydride into a reaction box body 100;
s220: an inert atmosphere, controlling the suction pipe 120 to suck air, and continuously injecting inert gas into the reaction chamber 100 through the gas injection pipe 130;
s230: stirring reaction, controlling the heating shell 200 to be heated to 220-260 ℃, and then starting the driving motor 300, so that the stirring shaft 400 drives the stirring blade 500 to stir, and setting the time to be 45-50 minutes.
The technical scheme in the embodiment of the application at least has the following technical effects or advantages:
the components of the unsaturated polyester resin can be uniformly and fully mixed together, and the temperature, time and pressure parameters in the reaction process can be accurately monitored, so that the preparation is more reasonable and effective.
Example III
In the above embodiment, the reaction rate between the mixed materials is faster and faster along with the increase of the temperature, so that the stirring efficiency needs to be increased to match the reaction rate, and the stirring blades 500 in the existing reactor are fixedly arranged and cannot be changed along with the increase of the temperature; the embodiment of the application is optimized to a certain extent on the basis of the embodiment.
As shown in fig. 4, 5 and 6, the stirring vane 500 includes a housing 510, a regulating chamber 520, an inner vane 530, a clamping block 540 and an inner spring 550; the whole shell 510 is a cylinder which is horizontally arranged, and the shell 510 is fixed on the stirring shaft 400; a plurality of adjusting cavities 520 are uniformly formed in the shell 510 along the length direction, and the top end and the bottom end of the adjusting cavities 520 are provided with identical rectangular openings; two inner blades 530 are arranged in each adjusting cavity 520, and the inner blades 530 and the clamping blocks 540 are in one-to-one correspondence; the two inner blades 530 are respectively and slidably connected in the upper end and the lower end openings of the adjusting cavity 520, and high temperature resistant sealing rings for sealing are arranged between the upper end and the lower end openings of the adjusting cavity 520 and the outer wall of the inner blades 530; the opposite surfaces of the two inner blades 530 in the same adjusting cavity 520 are both fixed with a limiting clamping block 540, and the width of the clamping block 540 is larger than the width of the upper end opening of the adjusting cavity 520; at least two internal springs 550 are fixed between the two clamping blocks 540 in the same adjusting cavity 520; when the linear distance between the two corresponding clamping blocks 540 is the largest, the internal pressure spring 550 is in a normal state.
Preferably, the inner blade 530 is made of stainless steel.
The technical scheme in the embodiment of the application at least has the following technical effects or advantages:
by arranging the inner blades 530, the inner blades 530 are retracted inside the adjusting cavity 520 under the interference of the mixed materials in the reactor before stirring, so that the inner blades 530 are damaged when the mixed materials in the reactor are more viscous; as the temperature increases, the rate of reaction between the mix becomes faster and faster, and the mix becomes less viscous, at which point the inner vanes 530 slowly extend out of the conditioning chamber 520 to increase the mixing efficiency.
Example IV
In the above embodiment, the extension length of the inner blade 530 is automatically adjusted only by the temperature and the viscosity degree of the mixture, so that the adaptation scene is limited and cannot be actively controlled; the embodiment of the application is optimized to a certain extent on the basis of the embodiment.
As shown in fig. 7, an inner magnetic member 560 is further fixed in the middle position inside the adjusting chamber 520, and the inner magnetic member 560 is a rectangular solid disposed horizontally as a whole; the inner magnetic member 560 is a dc electromagnet, and the magnetic poles of the inner magnetic member 560 are located at the upper and lower ends; the clamping blocks 540 are permanent magnets, and the magnetic poles of the opposite faces of the two clamping blocks 540 in the same adjusting cavity 520 are the same; after the temperature inside the adjusting chamber 520 increases, the magnetism of the inner magnetic member 560 and the latch block 540 is weakened as the temperature increases, so that the inner blade 530 can extend out of the housing 510.
Preferably, the thickness of the inner magnetic member 560 is no more than 10 cm.
As shown in fig. 8 and 9, step S230 in this embodiment includes:
s231: heating, namely controlling the heating shell 200 to be heated to 220-260 ℃;
s232: adjusting, starting the inner magnetic piece 560, enabling the inner magnetic piece 560 and the clamping block 540 to magnetically attract each other, further controlling the inner blade 530 to be in a retracted state, and then starting the driving motor 300, and setting the time to be 45-50 minutes;
s233: automatically adjusting, as the temperature inside the mixture increases, the magnetism of the inner magnetic member 560 and the fixture block 540 is weakened, so that the magnetic attraction between the inner magnetic member 560 and the fixture block 540 is reduced, and the inner blade 530 gradually extends out of the housing 510, so as to improve the stirring efficiency;
s234: actively adjusting, actively adjusting the magnetic magnitude of the inner magnetic member 560 to actively control the extension degree of the inner vane 530.
The technical scheme in the embodiment of the application at least has the following technical effects or advantages:
by arranging the inner magnetic piece 560, the extension length of the inner blade 530 can be freely controlled, so that the stirring efficiency can be effectively controlled in the reaction process; the multiple adjusting modes are more flexible and rich, and the adaptation scene is wider.
Example five
In the above embodiments, the mixed materials in the reactor cannot be effectively mixed in the vertical direction, and there is room for further improvement in the stirring process; the embodiment of the application is optimized to a certain extent on the basis of the embodiment.
As shown in fig. 10, the housing 510 includes a plurality of rotating units 511 and a plurality of rotating parts 512; the number of the rotating units 511 is the same as that of the adjusting chambers 520, the rotating units 511 are hollow cylinders, the adjusting chambers 520 are the inner spaces of the corresponding rotating units 511, and the inner blades 530 are connected to the corresponding rotating units 511 in a sliding manner; a rotating part 512 is rotatably connected between two adjacent rotating units 511, and one rotating unit 511 on the housing 510 near the stirring shaft 400 is fixed on the stirring shaft 400.
Preferably, the number of the rotating parts 512 on the housing 510 is 5 to 10.
Preferably, the rotating unit 511 and the rotating portion 512 are made of stainless steel.
Further, as shown in fig. 11, 12 and 13, two arc-shaped nets 570 are symmetrically fixed between the two inner blades 530 on the same rotating unit 511, and the arc-shaped nets 570 are made of stainless steel net; two of the curved nets 570 are located outside the corresponding rotating unit 511, and the concave surfaces of the curved nets 570 face the corresponding rotating unit 511.
Preferably, the arc length of the arc net 570 is not less than three-half of the diameter of the rotation unit 511.
Preferably, the mesh diameter of the curved net 570 is 5 to 10 cm.
As shown in fig. 12, 13 and 13, another step S230 in the present embodiment includes:
s231: heating, namely controlling the heating shell 200 to be heated to 220-260 ℃;
s232: adjusting, starting the inner magnetic piece 560, enabling the inner magnetic piece 560 and the clamping block 540 to magnetically attract each other, further controlling the inner blade 530 to be in a retracted state, and then starting the driving motor 300, and setting the time to be 45-50 minutes;
s233: the magnetic size of the inner magnetic member 560 is continuously changed by the control of the control unit to continuously change the extension length of the inner blade 530, and the arc-shaped net 570 is driven to vibrate and stir the mixture inside the reaction box 100, so as to improve the stirring efficiency.
The technical scheme in the embodiment of the application at least has the following technical effects or advantages:
by arranging the rotating unit 511 and the rotating part 512, the rotating unit 511 rotates along the rotating part 512 in the rotating process of the shell 510, so that the mixed materials in the reaction box 100 are controlled to flow and exchange in the vertical direction, and the reaction efficiency of the materials in the reactor is higher; through setting up arc net 570, further driven the inside mixed material of reaction box 100 and flowed and exchanged in vertical direction, arc net 570 sieves and breaks up the mixed material of part simultaneously and mixes, has reduced the probability of mixed material caking, has further improved the stirring effect and the reaction effect of the inside material of reactor.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The heat-resistant unsaturated polyester resin is characterized by comprising the following components in parts by weight:
42 to 47 parts by weight of phthalic anhydride, 8 to 11 parts by weight of maleic anhydride, 23 to 35 parts by weight of isophthalic acid, 57 to 62 parts by weight of diethylene glycol, 15 to 25 parts by weight of propylene glycol, 3.8 to 4.7 parts by weight of a catalyst, 1.5 to 4 parts by weight of benzoic acid, 19 to 22 parts by weight of fumaric anhydride, 0.7 to 1.2 parts by weight of a polymerization inhibitor, 1.1 to 2.6 parts by weight of triphenyl phosphate, 0.3 to 0.7 part by weight of a promoter cobalt iso-octoate, 1.1 to 1.5 parts by weight of an antioxidant, 0.4 to 0.6 part by weight of a light stabilizer and 2.5 to 3.8 parts by weight of a curing agent methyl ethyl ketone peroxide;
wherein the catalyst is prepared by mixing ethylene glycol antimony, dimethyl tin and tetraphenyl tin according to a molar ratio of 1:1:4; the polymerization inhibitor is prepared by mixing hydroquinone, hydroquinone and p-benzoquinone according to the weight ratio of 6:1:2.
2. A method for preparing heat-resistant unsaturated polyester resin, matching with the heat-resistant unsaturated polyester resin according to claim 1, comprising:
s100: premixing, namely adding phthalic anhydride, maleic anhydride, isophthalic acid, diethylene glycol, propylene glycol and a catalyst into a reactor, starting stirring and slowly heating to 330-410 ℃, and carrying out heat preservation reaction for 50-90 minutes;
s200: after the reaction is finished, the temperature is reduced to 80 to 120 ℃ and benzoic acid and fumaric acid anhydride are added, inert gas is introduced, stirring is started, the temperature is increased to 220 to 260 ℃ for polymerization, and the polymerization time is 45 to 50 minutes; s300: after the secondary mixing, closing an inert gas valve, reducing the temperature to 75-90 ℃, adding a polymerization inhibitor and a stabilizer, heating to 130-180 ℃ and stirring for 60-90 minutes;
s400: mixing for three times, adding the accelerator cobalt iso-octoate, stirring and heating to 130-150 ℃, wherein the stirring time is 45-70 minutes, adding the antioxidant II and the light stabilizer, stirring again for 60-90 minutes, and taking out after stirring is completed;
s500: baking, namely placing the obtained material into a baking oven for baking for 30-45 minutes, setting the temperature of the baking oven to be 90-105 ℃, taking out the baked material and placing the baked material into a clean reactor;
s600: mixing four times, adding the curing agent methyl ethyl ketone peroxide, and starting stirring, wherein the stirring temperature is 30-45 ℃, and the stirring time is 45-70 minutes;
s700: and (3) curing, namely placing the mixture into a curing furnace for curing after stirring, wherein the curing temperature is 85-95 ℃ and the curing time is 9-12 hours, and thus obtaining the heat-resistant flame-retardant unsaturated polyester resin.
3. The method for producing a heat-resistant unsaturated polyester resin according to claim 2, wherein the reactor comprises a reaction tank (100), a heating shell (200), and a stirring device; the reaction box body (100) is a hollow cylinder which is vertically arranged, the heating shell (200) is a round tube which is vertically arranged, and the heating shell (200) is sleeved on the reaction box body (100); the heating shell (200) has the functions of temperature detection, temperature setting and timing reminding; the top end of the reaction box body (100) is provided with a sealing cover (110) for placing materials and a gas injection pipe (130) for injecting inert gas, the top of the side wall of the reaction box body (100) is provided with a suction pipe (120) for exhausting, and the bottom of the side wall of the reaction box body (100) is provided with a discharge pipe (140); the stirring device comprises a driving motor (300), a stirring shaft (400) and a plurality of stirring blades (500), wherein the driving motor (300) is fixed at the top of the reaction box body (100), and the positions of the sealing cover (110) and the suction pipe (120) are staggered with the driving motor (300); a motor shaft of the driving motor (300) penetrates through a shell of the reaction box body (100) and stretches into the reaction box body (100), and the motor shaft of the driving motor (300) is fixedly connected with the stirring shaft (400); the stirring shaft (400) and the motor shaft of the driving motor (300) are vertically arranged, a plurality of stirring blades (500) are uniformly fixed on the stirring shaft (400), and the whole stirring blades (500) are horizontally arranged cylinders; the length of the stirring blade (500) is not less than two thirds of the inner radius of the reaction box body (100).
4. The method for producing a heat-resistant unsaturated polyester resin according to claim 3, wherein step S200 comprises: s210: placing materials, cooling to 80-120 ℃, opening a sealing cover (110) and placing benzoic acid and fumaric anhydride into a reaction box body (100);
s220: the inert atmosphere controls the suction pipe (120) to suck air, and simultaneously, the inert gas is continuously injected into the reaction box body (100) through the gas injection pipe (130);
s230: stirring reaction, controlling the heating shell (200) to be heated to 220-260 ℃, and then starting the driving motor (300) to enable the stirring shaft (400) to drive the stirring blade (500) to stir, and setting the time to be 45-50 minutes.
5. The method for preparing a heat resistant unsaturated polyester resin according to claim 4, wherein the stirring blade (500) comprises a housing (510), a regulating chamber (520), an inner blade (530), a fixture block (540), and an inner spring (550); the whole shell (510) is a cylinder which is horizontally arranged, and the shell (510) is fixed on the stirring shaft (400); a plurality of adjusting cavities (520) are uniformly formed in the shell (510) along the length direction, and the top end and the bottom end of each adjusting cavity (520) are provided with the same rectangular openings; two inner blades (530) are arranged in each adjusting cavity (520), and the inner blades (530) and the clamping blocks (540) are in one-to-one correspondence; the two inner blades (530) are respectively and slidably connected in the upper end opening and the lower end opening of the adjusting cavity (520), and high-temperature-resistant sealing rings for sealing are arranged between the upper end opening and the lower end opening of the adjusting cavity (520) and the outer wall of the inner blade (530); two opposite surfaces of the inner blades (530) in the same adjusting cavity (520) are respectively fixed with a clamping block (540) for limiting, and the width of the clamping block (540) is larger than that of an opening at the upper end of the adjusting cavity (520); at least two internal pressure springs (550) are fixed between two clamping blocks (540) in the same adjusting cavity (520); when the linear distance between the two corresponding clamping blocks (540) is maximum, the internal pressure spring (550) is in a normal state.
6. The method for preparing heat-resistant unsaturated polyester resin according to claim 5, wherein an inner magnetic member (560) is further fixed at a middle position inside the adjusting chamber (520), and the inner magnetic member (560) is integrally formed as a rectangular parallelepiped arranged horizontally; the inner magnetic piece (560) is a direct current electromagnet, and the magnetic poles of the inner magnetic piece (560) are positioned at the upper end and the lower end; the clamping blocks (540) are permanent magnets, and the magnetic poles of the opposite surfaces of the two clamping blocks (540) in the same adjusting cavity (520) are the same.
7. The method of preparing heat-resistant unsaturated polyester resin according to claim 6, wherein step S230 comprises:
s231: heating, namely controlling the heating shell (200) to heat to 220-260 ℃;
s232: adjusting, starting the inner magnetic piece (560) to enable the inner magnetic piece (560) and the clamping block (540) to be mutually magnetically attracted, further controlling the inner blade (530) to be in a retracted state, and then starting the driving motor (300), and setting the time to be 45-50 minutes;
s233: the automatic adjustment, along with the temperature rise in the mixture, the magnetism of the inner magnetic piece (560) and the clamping block (540) is weakened, so that the magnetic attraction between the inner magnetic piece (560) and the clamping block (540) is reduced, and the inner blade (530) gradually extends out of the shell (510) to improve the stirring efficiency;
s234: actively adjusting the magnetic magnitude of the inner magnetic member (560) to actively control the extension degree of the inner blade (530).
8. The method of producing a heat resistant unsaturated polyester resin according to claim 6, wherein said housing (510) comprises a plurality of rotating units (511) and a plurality of rotating parts (512); the rotating units (511) and the adjusting cavities (520) are the same in number and correspond to each other one by one, the rotating units (511) are hollow cylinders as a whole, the adjusting cavities (520) are inner spaces of the corresponding rotating units (511), and the inner blades (530) are connected to the corresponding rotating units (511) in a sliding mode; a rotating part (512) is rotatably connected between two adjacent rotating units (511), and one rotating unit (511) on the shell (510) close to the stirring shaft (400) is fixed on the stirring shaft (400).
9. The method for preparing a heat resistant unsaturated polyester resin according to claim 8, wherein two arc-shaped nets (570) are symmetrically fixed between two inner blades (530) on the same rotating unit (511), and the arc-shaped nets (570) are made of stainless steel net; the two arc-shaped nets (570) are positioned outside the corresponding rotating units (511), and the concave surfaces of the arc-shaped nets (570) face to the corresponding rotating units (511).
10. The method of preparing heat-resistant unsaturated polyester resin according to claim 9, wherein step S230 comprises:
s231: heating, namely controlling the heating shell (200) to heat to 220-260 ℃;
s232: adjusting, starting the inner magnetic piece (560) to enable the inner magnetic piece (560) and the clamping block (540) to be mutually magnetically attracted, further controlling the inner blade (530) to be in a retracted state, and then starting the driving motor (300), and setting the time to be 45-50 minutes;
s233: vibration stirring, the magnetic size of the inner magnetic piece (560) is continuously changed through the control of the control unit, so that the extending length of the inner blade (530) is continuously changed, and the arc-shaped net (570) is driven to vibrate and stir the mixture inside the reaction box body (100) so as to improve stirring efficiency.
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