CN110577718B - Aniline modified phenolic molding plastic for low-voltage electrical apparatus and preparation method thereof - Google Patents
Aniline modified phenolic molding plastic for low-voltage electrical apparatus and preparation method thereof Download PDFInfo
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- CN110577718B CN110577718B CN201911044100.3A CN201911044100A CN110577718B CN 110577718 B CN110577718 B CN 110577718B CN 201911044100 A CN201911044100 A CN 201911044100A CN 110577718 B CN110577718 B CN 110577718B
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 238000000465 moulding Methods 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000004033 plastic Substances 0.000 title abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 32
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000005011 phenolic resin Substances 0.000 claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 229920001187 thermosetting polymer Polymers 0.000 claims abstract description 21
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 20
- 239000003365 glass fiber Substances 0.000 claims abstract description 19
- -1 aniline modified phenolic resin Chemical class 0.000 claims abstract description 17
- 239000007822 coupling agent Substances 0.000 claims abstract description 17
- 159000000003 magnesium salts Chemical class 0.000 claims abstract description 16
- 239000011521 glass Substances 0.000 claims abstract description 12
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000000347 magnesium hydroxide Substances 0.000 claims abstract description 12
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 10
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 8
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 59
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- WGKLIJDVPACLGG-UHFFFAOYSA-N trizinc diborate hydrate Chemical compound O.[Zn++].[Zn++].[Zn++].[O-]B([O-])[O-].[O-]B([O-])[O-] WGKLIJDVPACLGG-UHFFFAOYSA-N 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 7
- 239000000206 moulding compound Substances 0.000 claims description 7
- 229920003986 novolac Polymers 0.000 claims description 7
- 208000005156 Dehydration Diseases 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 6
- 238000006297 dehydration reaction Methods 0.000 claims description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 5
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000003677 Sheet moulding compound Substances 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical group C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 3
- 239000008116 calcium stearate Substances 0.000 claims description 3
- 235000013539 calcium stearate Nutrition 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 3
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 abstract description 13
- 230000000052 comparative effect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- WMWXXXSCZVGQAR-UHFFFAOYSA-N dialuminum;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3] WMWXXXSCZVGQAR-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 239000011810 insulating material Substances 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
- 238000012360 testing method Methods 0.000 description 2
- 229920005992 thermoplastic resin Polymers 0.000 description 2
- 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 description 1
- 229920001342 Bakelite® Polymers 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000004637 bakelite Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000012778 molding material Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
- C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08L61/14—Modified phenol-aldehyde condensates
-
- 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
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- 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
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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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)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides an aniline modified phenolic moulding plastic for low-voltage apparatuses and a preparation method thereof, wherein the aniline modified phenolic moulding plastic for low-voltage apparatuses comprises the following components in parts by weight: 5-20 parts of thermoplastic phenolic resin; 5-25 parts of thermosetting aniline modified phenolic resin; 10-30 parts of magnesium salt whiskers; 10-25 parts of magnesium hydroxide; 2-10 parts of hydrated zinc borate; 10-25 parts of glass fiber; 5-20 parts of low-melting-point glass powder; 1-5 parts of a curing agent; 0.1-1 part of a coupling agent; 1-2 parts of a release agent. The aniline modified phenolic molding compound for the low-voltage electric appliance has the characteristics of high strength, high heat resistance, CTI (comparative tracking index) grade of 2, stability, difficult fluctuation, excellent insulating property and flame resistance and the like, can meet the requirements of special products such as the automobile industry and household electric appliances, and is particularly suitable for accessory products with special requirements on the insulating property and the tracking resistance.
Description
Technical Field
The invention relates to an aniline modified phenolic molding compound for a low-voltage apparatus and a preparation method thereof, belonging to the technical field of composite materials.
Background
Phenolic molding compound, also called bakelite powder, is generally composed of phenolic resin, inorganic filler, toughening and reinforcing material, curing agent urotropine, pigment and the like, and is a common thermosetting plastic. The phenolic moulding plastic has the advantages of wide raw material sources, relatively simple production process and equipment, good heat resistance, high mechanical strength, electrical insulation, high temperature resistance, excellent creep property, low price and good molding processability of products, particularly the fiber reinforced phenolic moulding plastic of glass fiber, cotton fiber and the like has better mechanical strength, and has wide application in the aspects of automobiles, metallurgy, consumer electronics, aerospace and the like.
The process of gradually forming a conductive path on the surface of the solid insulating material under the combined action of an electric field and an electrolyte is called tracking. And the ability of the surface of the insulating material to resist tracking is referred to as tracking resistance. The development of tracking in polymer insulation is determined by the formation and accumulation of free carbon on the surface of the material. The phenolic molding compound is easy to form a conductive substance similar to a graphite structure after being electrically scratched due to the aromatic molecular structure of the phenolic resin, so that a conductive path is easily formed on the surface of the material, and the tracking resistance of the phenolic molding compound is poor (generally, CTI is less than or equal to 175V). When the phenolic molding compound is used for low-voltage electrical appliance accessories, particularly, the CTI grade of partial product application requirements can reach 2 grade, and the existing phenolic molding compound can not reach the requirements.
Chinese patent publication No. CN 102020827A discloses phenolic molding compound for low-voltage electric appliances, and specifically discloses that thermosetting resin (one or more of melamine formaldehyde resin, epoxy resin and unsaturated resin) is introduced into phenolic molding compound, so as to improve tracking resistance of material.
Chinese patent (publication No. CN 103087465A) discloses a phenolic resin molding compound, in particular a phenolic resin molding compound which mainly comprises phenolic resin, glass fiber, magnesium hydroxide, zinc borate, aluminum oxide monohydrate and other auxiliary agents. However, as a result of long-term practice and empirical data, it is difficult to obtain a phenolic resin molding compound with a stable CTI rating of 2, which has a tracking resistance, by adding a large amount of glass fibers to improve the mechanical strength of the material and only by adding a certain proportion of flame retardants (such as magnesium hydroxide, zinc borate and aluminum oxide monohydrate).
Disclosure of Invention
The invention aims to provide the phenolic moulding plastic with the characteristics of high strength, high heat resistance, stability and difficult fluctuation, excellent insulating property, excellent flame resistance and the like, and the CTI grade reaches 2.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides an aniline modified phenolic moulding plastic for a low-voltage apparatus, which consists of the following components in parts by weight:
in a preferred embodiment of the invention, the phenolic novolac resin is an acid-catalyzed phenolic novolac resin, wherein the phenol/formaldehyde molar ratio is 1: 0.75-0.86 percent, less than or equal to 5.0 percent of free phenol, less than or equal to 1.0 percent of water, 40-80 s of polymerization speed and 50-80 mm of fluidity.
In a preferred embodiment of the invention, the magnesium salt whiskers are basic magnesium sulfate whiskers.
In a preferred embodiment of the invention, the hydrated zinc borate is 3.5 hydrated zinc borate.
In a preferred embodiment of the present invention, the glass fiber has a diameter of 10 to 13 μm and a length of 1 to 3 mm.
In a preferred embodiment of the present invention, the low-melting glass frit has a melting point of 500 to 900 ℃.
In a preferred embodiment of the present invention, the curing agent is urotropin.
In a preferred embodiment of the present invention, the coupling agent is selected from one or a combination of two of a silane coupling agent or a titanate coupling agent.
In a preferred embodiment of the invention, the release agent is selected from one or a combination of stearic acid, zinc stearate, calcium stearate or stearic acid amide.
The invention also provides a preparation method of the aniline modified phenolic molding compound, which comprises the following steps:
(1) mixing thermoplastic phenolic resin, thermosetting aniline modified phenolic resin, magnesium salt whisker, magnesium hydroxide, zinc borate hydrate, low-melting-point glass powder, a curing agent, a coupling agent and a release agent, crushing, adding glass fiber, and mixing;
(2) mixing the mixture obtained in the step (1) on a double-roll plasticator under the heating condition to form sheet molding compound, and finally granulating and forming to obtain aniline modified phenolic molding compound for low-voltage electrical appliances;
wherein the temperature of the operation roller is 80-90 ℃, the temperature of the idle roller is 130-140 ℃,
the preparation method of the thermosetting aniline modified phenolic resin comprises the following steps:
(a) phenol, aniline and ammonia water are mixed according to a molar ratio of 1: 0.5: 0.05 into a reaction kettle, and then adding formaldehyde into the reaction kettle according to the molar ratio of phenol to formaldehyde of 1: 1.7, putting into a reaction kettle, and uniformly stirring;
(b) heating the mixture obtained in the step (a) to 85 ℃, stopping heating, automatically heating the material to boiling, after reflux reaction for 70 minutes, gradually raising the vacuum degree to more than-0.095 Mpa, and dehydrating to obtain the thermosetting aniline modified phenolic resin, wherein the free phenol is less than or equal to 3.5, the water content is less than or equal to 1.0, and the polymerization speed is 70-110 s;
wherein the temperature of the mixture in the dehydration stage is 60-98 ℃.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the invention is further explained below.
The invention provides an aniline modified phenolic moulding plastic for a low-voltage apparatus, which consists of the following components in parts by weight:
in a preferred embodiment of the invention, the phenolic novolac resin is an acid-catalyzed phenolic novolac resin, wherein the phenol/formaldehyde molar ratio is 1: 0.75-0.86 percent, less than or equal to 5.0 percent of free phenol, less than or equal to 1.0 percent of water, 40-80 s of polymerization speed and 50-80 mm of fluidity. The invention adopts the matching use of the linear phenolic resin and the thermosetting aniline modified phenolic resin, and aims to improve the brittleness generated by simply adopting the thermosetting aniline modified phenolic resin, thereby improving the impact toughness of the material.
According to the invention, an aniline structure with smaller polarity is introduced into the molecular structure of the phenolic resin, so that the dielectric property and the arc resistance of the modified phenolic resin are improved, and the thermosetting aniline modified phenolic resin is synthesized, so that the heat resistance of the phenolic resin is improved, and the insulating property of the modified phenolic resin at high temperature is improved.
In a preferred embodiment of the invention, the magnesium salt whiskers are basic magnesium sulfate whiskers, and the chemical composition is as follows: MgSO4 & 5Mg (OH)2 & 3H2O, length L: 3.5-120 μm, diameter D: less than 2 μm. The magnesium salt whisker has high length-diameter ratio, is a reinforced fiber material, has a single crystal structure, and has obvious reinforcing, stiffening and flame-retardant effects. Because the magnesium salt whisker contains crystal water, the magnesium salt whisker is decomposed to separate out water molecules at high temperature generated during discharging in the process of electric marking, and carbon particles deposited on the surface of the material can be washed away by the formed steam airflow, so that the tracking resistance of the material is improved.
The magnesium salt whisker is adopted for the purpose of improving the tracking resistance of the material, on the one hand, the fiber structure is utilized for strengthening and toughening, so that partial glass fiber is replaced, the bridging phenomenon generated by excessive glass fiber in the mixing process of the phenolic molding compound is not difficult, the compatibility of the magnesium salt whisker and the phenolic resin is excellent, the production process of the phenolic molding compound is facilitated, and the production of the phenolic molding compound containing the glass fiber can be facilitated even under the condition that the matrix resin-phenolic resin component is reduced.
In a preferred embodiment of the present invention, the magnesium hydroxide has a fineness of 1000 to 5000 mesh. Because magnesium hydroxide is decomposed to separate out water molecules at high temperature generated during discharging in the process of electric tracking, carbon particles deposited on the surface of the material can be washed away by the formed water vapor airflow, and the electric tracking resistance of the material is favorably improved.
In a preferred embodiment of the invention, the hydrated zinc borate is 3.5 hydrated zinc borate, and the fineness is 1000-5000 meshes. The hydrated zinc borate is a low-melting-point compound, on one hand, the hydrated zinc borate is melted into a glass state substance to cover the surface of the material at high temperature generated during discharging in the process of electroscription, and plays a role in blocking a 'conductive path'; on the other hand, the high temperature decomposes the hydrated zinc borate to separate out water molecules, and the formed water vapor airflow can flush away carbon particles deposited on the surface of the material, thereby being beneficial to improving the tracking resistance of the material.
In a preferred embodiment of the present invention, the glass fiber has a diameter of 10 to 13 μm and a length of 1 to 3 mm. The glass fibers are added mainly to improve the mechanical strength of the material.
In a preferred embodiment of the invention, the low-melting-point glass powder has a melting temperature range of 500-900 ℃ and a fineness of 500-3000 meshes, and is melted into a glassy substance to cover the surface of a material at a high temperature generated during discharging in an electrotracking process, so that a 'conductive path' is sealed, and the anti-tracking performance of the material is improved.
In a preferred embodiment of the present invention, the curing agent is urotropin, which is a cross-linking agent for phenolic novolac resins.
In a preferred embodiment of the present invention, the coupling agent is selected from one or a combination of two of a silane coupling agent or a titanate coupling agent. The coupling agent is a substance with two functional groups with different properties, and the molecular structure of the coupling agent is mainly characterized in that the molecule contains two groups with different chemical properties, one group is an inorganophilic group and is easy to chemically react with the surface of an inorganic substance; the other is an organophilic group which is capable of chemically reacting with or forming hydrogen bonds soluble in synthetic resins or other polymers. Therefore, the coupling agent is called as a molecular bridge and is used for improving the interface action between inorganic matters and organic matters, so that the properties of the composite material, such as physical properties, electrical properties, thermal properties and the like, are greatly improved. The components of the invention are mostly mineral components except phenolic resin, and the addition of the coupling agent can improve the interface bonding effect of the phenolic resin and the mineral components, thereby improving the mechanical property, the electrical property, the heat resistance and the like of the phenolic molding compound.
In a preferred embodiment of the invention, the release agent is selected from one or a combination of stearic acid, zinc stearate, calcium stearate or stearic acid amide.
The invention also provides a preparation method of the aniline modified phenolic moulding compound for the low-voltage apparatus, which comprises the following steps:
(1) mixing thermoplastic phenolic resin, thermosetting aniline modified phenolic resin, magnesium salt whisker, magnesium hydroxide, zinc borate hydrate, low-melting-point glass powder, a curing agent, a coupling agent and a release agent, crushing, adding glass fiber, and mixing;
(2) mixing the mixture obtained in the step (1) on a double-roll plasticator under the heating condition to form sheet molding compound, and finally granulating and forming to obtain aniline modified phenolic molding compound for low-voltage electrical appliances;
wherein the temperature of the operation roller is 80-90 ℃, the temperature of the idle roller is 130-140 ℃,
the preparation method of the thermosetting aniline modified phenolic resin comprises the following steps:
(a) phenol, aniline and ammonia water are mixed according to a molar ratio of 1: 0.5: 0.05 into a reaction kettle, and then adding formaldehyde into the reaction kettle according to the molar ratio of phenol to formaldehyde of 1: 1.7, putting into a reaction kettle, and uniformly stirring;
(b) heating the mixture obtained in the step (a) to 85 ℃, stopping heating, automatically heating the material to boiling, after reflux reaction for 70 minutes, gradually raising the vacuum degree to more than-0.095 Mpa, and dehydrating to obtain the thermosetting aniline modified phenolic resin, wherein the free phenol is less than or equal to 3.5, the water content is less than or equal to 1.0, and the polymerization speed is 70-110 s;
wherein the temperature of the mixture in the dehydration stage is 60-98 ℃.
The invention adopts thermoplastic phenolic resin, thermosetting aniline modified phenolic resin, magnesium salt whisker, magnesium hydroxide, zinc borate hydrate, glass fiber, low-melting glass powder, curing agent, coupling agent, release agent and the like to prepare the aniline modified phenolic moulding compound for low-voltage electric appliances, and the phenolic moulding compound has the characteristics of high strength, high heat resistance, CTI (comparative tracking index) grade up to 2, stability, low possibility of fluctuation, excellent insulating property and flame resistance and the like, can meet the requirements of special products in the automobile industry, household electric appliances and the like, and is particularly suitable for accessory products with special requirements on insulating property and tracking resistance.
Examples
The present invention will be described in detail below by way of examples.
In the following examples 1 to 6, the parameters of the compositions for preparing aniline-modified phenolic moulding compounds for low-voltage applications were as follows:
the phenolic thermoplastic resin is an acid-catalyzed phenolic novolac resin, wherein the molar ratio of phenol/formaldehyde is 1: 0.75-0.86 percent, less than or equal to 5.0 percent of free phenol, less than or equal to 1.0 percent of water, 40-80 s of polymerization speed and 50-80 mm of fluidity;
the magnesium salt whisker is basic magnesium sulfate whisker, and has the chemical components as follows: MgSO (MgSO)4·5Mg(OH)2·3H2O, length L: 3.5-120 μm, diameter D: less than 2 μm;
the fineness of the magnesium hydroxide is 1000-5000 meshes;
the hydrated zinc borate is 3.5 hydrated zinc borate, and the fineness of the hydrated zinc borate is 1000-5000 meshes;
the diameter of the glass fiber is 10-13 μm, and the length of the glass fiber is 1-3 mm;
the low-melting-point glass powder has a melting point of 500-900 ℃ and a fineness of 500-3000 meshes.
The aniline-modified phenolic molding materials for low-voltage electric appliances in the following examples 1 to 6 were prepared as follows:
mixing thermoplastic phenolic resin, thermosetting aniline modified phenolic resin, magnesium salt whiskers, magnesium hydroxide, zinc borate hydrate, low-melting-point glass powder, a curing agent, a coupling agent and a release agent in a certain weight proportion, crushing, adding glass fiber, mixing again to uniformly mix the components, conveying the uniformly mixed materials to a double-roll plasticator by a conveying auger, shearing and extruding the materials due to the rotation speed difference of double rolls, mixing the materials on the double-roll plasticator under the heating condition (the temperature of an operation roll is 80-90 ℃, and the temperature of an idle roll is 130-140 ℃) to form sheet molding compounds, and finally granulating and molding to obtain the aniline modified phenolic molding compounds for low-voltage electric appliances.
The preparation method of the thermosetting aniline modified phenolic resin comprises the following steps:
phenol, aniline and ammonia water are mixed according to a molar ratio of 1: 0.5: 0.05 into a reaction kettle equipped with a reflux condenser, a stirrer, a heating device and a dehydration device; then, mixing formaldehyde according to the molar ratio of phenol to formaldehyde of 1: 1.7, putting into a reaction kettle, and uniformly stirring; heating to 85 ℃, stopping heating, automatically heating the materials to boiling, and carrying out reflux reaction for 70 minutes; then gradually raising the vacuum degree to be more than-0.095 Mpa, and dehydrating; when the temperature of the feed liquid is reduced to below 60 ℃ in the dehydration process, introducing steam into the jacket for heating, wherein the temperature of the feed liquid in the dehydration stage does not exceed 98 ℃, or immediately introducing cooling water into the jacket of the reaction kettle for cooling; dehydrating until the material liquid becomes thick until reaching the required polymerization speed, and obtaining the thermosetting aniline modified phenolic resin, wherein the technical indexes are that the free phenol is less than or equal to 3.5, the water content is less than or equal to 1.0, and the polymerization speed is 70-110 s.
Table 1 shows the compositions (in parts by weight) and performance indices of the phenolic molding compounds of examples 1-6. The test pieces for evaluation of properties were prepared by press molding under the following conditions: the preheating temperature is 95-115 ℃, the pressing mold temperature is 165-175 ℃, and the curing time is 1.0 min/mm.
TABLE 1
The evaluation of the properties of the phenolic moulding materials of examples 1 to 6 above was carried out as follows:
the measurements of the performance indexes in Table 1 were carried out in accordance with ISO 14526-2, and the flame retardancy test was carried out in accordance with UL 94.
Examples 1 to 6 were each prepared according to the formulation specified in the present invention using components such as a thermoplastic phenol resin, a thermosetting aniline-modified phenol resin, magnesium salt whiskers, magnesium hydroxide, zinc borate hydrate, glass fibers, a low-melting glass frit, a curing agent, a coupling agent, and a release agent. The resin ratios (sum of the thermoplastic resin and the thermosetting aniline-modified phenolic resin) of examples 1 to 3 were 30 parts by weight and the resin ratios of examples 4 to 6 were 26 parts by weight, and it can be seen that examples 4 to 6 had better CTI index and heat distortion temperature index than examples 1 to 3. The reason for this is that the resin content is reduced, i.e. the total amount of carbonizable substances is reduced, and the mineral content is increased to improve the heat resistance of the material, so that the CTI index and the heat distortion temperature index of the material are further improved.
As can be seen from Table 1, the phenolic molding compounds in the embodiments 1-6 of the present invention have the characteristics of high strength, high heat resistance, CTI level up to 2, stability and low possibility of fluctuation, and particularly excellent insulating property and flame resistance, and can meet the requirements of special products in the automobile industry and household appliances, and are particularly suitable for accessory products having special requirements for insulating property and tracking resistance. The invention has the significance that the obtained phenolic moulding compound has high strength, high heat resistance, CTI index, insulating property and flame resistance, solves the technical problem that the CTI index of the phenolic moulding compound is difficult to stably reach level 2, and also solves the process problem in production and processing.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, but that various changes and modifications may be made without departing from the spirit and scope of the invention, and such changes and modifications are within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (9)
1. The aniline modified phenolic molding compound for the low-voltage electric appliance is characterized by comprising the following components in parts by weight:
wherein the magnesium salt whiskers are basic magnesium sulfate whiskers.
2. The aniline modified phenolic molding compound for low-voltage electric appliances according to claim 1, wherein the thermoplastic phenolic resin is an acid-catalyzed phenol novolac resin, wherein the molar ratio of phenol/formaldehyde is 1: 0.75-0.86 percent, less than or equal to 5.0 percent of free phenol, less than or equal to 1.0 percent of water, 40-80 s of polymerization speed and 50-80 mm of fluidity.
3. The aniline modified phenolic molding compound for low-voltage electric appliances according to claim 1, wherein the zinc borate hydrate is 3.5 zinc borate hydrate.
4. The aniline modified phenolic molding compound for low-voltage apparatuses as claimed in claim 1, wherein the glass fiber has a diameter of 10 to 13 μm and a length of 1 to 3 mm.
5. The aniline modified phenolic molding compound for low-voltage apparatuses as claimed in claim 1, wherein the melting point of the low-melting-point glass powder is 500-900 ℃.
6. The aniline modified phenolic molding compound for low-voltage electric appliances according to claim 1, wherein the curing agent is urotropin.
7. The aniline modified phenolic molding compound for low-voltage apparatuses according to claim 1, wherein the coupling agent is selected from one or a combination of two of silane coupling agent and titanate coupling agent.
8. The aniline modified phenolic molding compound for low-voltage electric appliances according to claim 1, wherein the release agent is one or more of stearic acid, zinc stearate, calcium stearate or stearic acid amide.
9. The process for preparing an aniline modified phenolic moulding compound according to any one of claims 1 to 8, comprising the steps of:
(1) mixing thermoplastic phenolic resin, thermosetting aniline modified phenolic resin, magnesium salt whisker, magnesium hydroxide, zinc borate hydrate, low-melting-point glass powder, a curing agent, a coupling agent and a release agent, crushing, adding glass fiber, and mixing;
(2) mixing the mixture obtained in the step (1) on a double-roll plasticator under the heating condition to form sheet molding compound, and finally granulating and forming to obtain aniline modified phenolic molding compound for low-voltage electrical appliances;
wherein the temperature of the operation roller is 80-90 ℃, the temperature of the idle roller is 130-140 ℃,
the preparation method of the thermosetting aniline modified phenolic resin comprises the following steps:
(a) phenol, aniline and ammonia water are mixed according to a molar ratio of 1: 0.5: 0.05 was charged to a reaction kettle, and then formaldehyde was added in a molar ratio of phenol to formaldehyde of 1: 1.7, putting into a reaction kettle, and uniformly stirring;
(b) heating the mixture obtained in the step (a) to 85 ℃, stopping heating, automatically heating the material to boiling, after reflux reaction for 70 minutes, gradually raising the vacuum degree to more than-0.095 Mpa, and dehydrating to obtain the thermosetting aniline modified phenolic resin, wherein the free phenol is less than or equal to 3.5, the water content is less than or equal to 1.0, and the polymerization speed is 70-110 s;
wherein the temperature of the mixture in the dehydration stage is 60-98 ℃.
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Denomination of invention: An aniline modified phenolic molding compound for low-voltage electrical appliances and its preparation method Granted publication date: 20220520 Pledgee: Shanghai Rural Commercial Bank Co.,Ltd. Jinshan sub branch Pledgor: Shanghai Eurasian synthetic materials Co.,Ltd. Registration number: Y2024310000622 |