CN108148362B - Composition with internal and external lubricating effect for PA engineering plastic - Google Patents
Composition with internal and external lubricating effect for PA engineering plastic Download PDFInfo
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- CN108148362B CN108148362B CN201711481344.9A CN201711481344A CN108148362B CN 108148362 B CN108148362 B CN 108148362B CN 201711481344 A CN201711481344 A CN 201711481344A CN 108148362 B CN108148362 B CN 108148362B
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- 239000000203 mixture Substances 0.000 title claims abstract description 44
- 229920006351 engineering plastic Polymers 0.000 title claims abstract description 26
- 230000001050 lubricating effect Effects 0.000 title claims abstract description 17
- -1 fatty acid salt Chemical class 0.000 claims abstract description 37
- 239000006229 carbon black Substances 0.000 claims abstract description 32
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 20
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 18
- 239000000194 fatty acid Substances 0.000 claims abstract description 18
- 229930195729 fatty acid Natural products 0.000 claims abstract description 18
- 150000002148 esters Chemical class 0.000 claims abstract description 10
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 230000000694 effects Effects 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims description 22
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 14
- 150000004665 fatty acids Chemical class 0.000 claims description 11
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 9
- 239000008116 calcium stearate Substances 0.000 claims description 9
- 235000013539 calcium stearate Nutrition 0.000 claims description 9
- 235000011037 adipic acid Nutrition 0.000 claims description 7
- 239000001361 adipic acid Substances 0.000 claims description 7
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 7
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- 238000005461 lubrication Methods 0.000 claims description 6
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 5
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 claims description 4
- 239000004593 Epoxy Substances 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 2
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 2
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims 2
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 claims 1
- 229940063655 aluminum stearate Drugs 0.000 claims 1
- 229940078456 calcium stearate Drugs 0.000 claims 1
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 claims 1
- 235000019359 magnesium stearate Nutrition 0.000 claims 1
- 229940057948 magnesium stearate Drugs 0.000 claims 1
- 229940114930 potassium stearate Drugs 0.000 claims 1
- ANBFRLKBEIFNQU-UHFFFAOYSA-M potassium;octadecanoate Chemical compound [K+].CCCCCCCCCCCCCCCCCC([O-])=O ANBFRLKBEIFNQU-UHFFFAOYSA-M 0.000 claims 1
- 229940080350 sodium stearate Drugs 0.000 claims 1
- 229940057977 zinc stearate Drugs 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- 230000001976 improved effect Effects 0.000 abstract description 9
- 239000011347 resin Substances 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 239000000945 filler Substances 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 239000000314 lubricant Substances 0.000 description 59
- 238000012360 testing method Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 238000001125 extrusion Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 9
- 239000004033 plastic Substances 0.000 description 9
- 238000001746 injection moulding Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000003365 glass fiber Substances 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 241000872198 Serjania polyphylla Species 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000008431 aliphatic amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000005076 polymer ester Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009757 thermoplastic moulding Methods 0.000 description 1
- 239000001993 wax 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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses a composition with an internal and external lubricating effect for PA engineering plastics, which comprises the following components in percentage by mass: 40-80% of high molecular weight fatty acid-adipic acid-pentaerythritol polymerized composite ester as the component A, 10-30% of higher fatty acid salt as the component B, 10-30% of polar group-containing ultrahigh molecular weight polysiloxane as the component C and 2-15% of modified white carbon black as the component D. When the composition with the internal and external lubricating effect is applied to PA engineering plastics, the demolding effect of a product can be effectively improved, the fluidity of the resin in the melting processing process is improved, the dispersion of the filler is promoted, the surface gloss and the smoothness of the product are improved, and the mechanical property is basically not influenced.
Description
The technical field is as follows:
the invention relates to the field of plastic processing, in particular to a composition with an internal and external lubricating effect for PA engineering plastics.
Background art:
in the plastic processing and injection molding process, especially for PA engineering plastics, good fluidity and demolding performance are important guarantees for improving the processing speed of plastic products and improving the yield.
However, during the melting process of PA engineering plastics, the friction between the plastic melts and between the plastic melt and the metal screw can cause the fluidity of the molten plastics to be reduced. In addition, the PA engineering plastic has higher polarity than that of common polyolefin, and is easy to be mechanically bonded with metal in the injection molding process, so that the injection molding part has poor demolding performance. In order to improve the processing fluidity, improve the demoulding effect and facilitate the plastic processing, the lubricant with the internal and external lubricating function becomes an indispensable means. The common PA engineering plastic lubricant comprises various waxes, fatty acids, metal soaps, aliphatic amides and the like. However, these lubricants have the disadvantage that they either only increase the flowability of the PA, or only have good release properties, or have an influence on the mechanical properties of the article.
The invention content is as follows:
the invention aims to overcome the defects of the prior art and provide a lubricant for PA engineering plastics, which can effectively improve the fluidity in the PA extrusion processing process, reduce the adhesive force between a workpiece and a metal mold in the injection molding process, improve the demolding effect, promote the filler dispersion, improve the surface gloss and smoothness of the product and basically has no influence on the mechanical properties of the PA engineering plastics compared with the conventional PA engineering plastics used at present.
In order to achieve the purpose, the invention adopts the following technical scheme:
a composition with internal and external lubrication function for PA engineering plastics comprises the following components in percentage by mass:
and (2) component A: 40-80% of high molecular weight fatty acid-adipic acid-pentaerythritol polymerized composite ester;
and (B) component: 10-30% of higher fatty acid salt;
and (3) component C: polar group-containing ultrahigh molecular weight polysiloxane 10-30%;
and (3) component D: 2-15% of modified white carbon black;
the sum of the mass percentages of the components is 100 percent.
Preferably, the polymeric complex ester of high molecular fatty acid-adipic acid-pentaerythritol provided by the invention is prepared by reacting fatty acid, adipic acid and pentaerythritol to obtain a product having a structure shown as formula i:
preferred R is C10-C30N is a natural number of 1 to 30; particularly preferred R is C16-C18Fatty acyl, n is a natural number from 5 to 15.
In the invention, the molar ratio of fatty acid to adipic acid to pentaerythritol in the high molecular weight fatty acid-adipic acid-pentaerythritol polymerized composite ester is preferably 2-2.2:1:0.45-0.495, and particularly preferably 2-2.1:1: 0.45-0.475.
In the present invention, the higher fatty acid salt is preferably one or a mixture of more of sodium stearate, calcium stearate, barium stearate and zinc stearate, and particularly preferably one or a mixture of more of calcium stearate, zinc stearate and barium stearate.
As the optimization of the technical proposal, the structure of the polar group-containing ultrahigh molecular weight polysiloxane is shown as a formula II and is a block copolymer of … AAAAA-BBBBBB-AAA-BBBB ….
In the present invention, the viscosity-average molecular weight of the polar group-containing ultrahigh molecular weight polysiloxane is preferably 20 to 50 ten thousand, and particularly preferably 20 to 30 ten thousand.
In the present invention, the polar group-containing ultra-high molecular weight polysiloxane side chain group R is preferably one of a ureido group, a cyano group, an epoxy quaternary ammonium salt group, an amino group, a carboxyl group and a hydroxyl group, and particularly preferably the side chain polar group R is one of a ureido group, a carboxyl group and an amino group.
In the present invention, the number of polar groups R in the polar group-containing ultra-high molecular weight polysiloxane side chains preferably accounts for 2% or more of the total number of side chains, and more preferably the number of polar groups R in the side chains accounts for 5% or more of the total number of side chains.
As the technical scheme, the particle size range of the modified white carbon black is preferably 10nm-100 μm, and the particularly preferred particle size range of the modified white carbon black is 100nm-10 μm.
Preferably, in the technical scheme, the modified white carbon black is one or a mixture of more of organochlorosilane modified white carbon black, siloxane modified white carbon black, silane coupling agent modified white carbon black and alcohol ester modified white carbon black, and particularly, the modified white carbon black is one or a mixture of two of siloxane modified white carbon black and silane coupling agent modified white carbon black.
The preparation method of the composition with the internal and external lubricating effect for the PA engineering plastic comprises the following steps: firstly, stirring and mixing modified white carbon black and polar group-containing ultrahigh molecular weight polysiloxane at high speed for 5-10min at room temperature to prepare particles/powder, and then stirring and mixing the particles/powder with high molecular weight fatty acid-adipic acid-pentaerythritol polymeric ester and higher fatty acid salt at high speed for 5-10min at room temperature to prepare particles/powder.
The invention has the following beneficial effects:
the demolding performance is good: when the composition with the internal and external lubricating effect is added into PA engineering plastic for injection molding, a layer of lubricant film is formed between resin and a metal mold, so that the adhesive force between molten PA resin and the metal mold can be effectively reduced, and the demolding is improved.
The processing fluidity is good: the composition with the internal and external lubricating effect for the PA engineering plastic is added into the PA engineering plastic, so that the viscosity of resin melt can be effectively reduced and the dispersion of fillers can be promoted during screw extrusion processing.
The surface glossiness and the smoothness are good: the surface gloss and smoothness of an injection molding product can be obviously improved by adding the composition with the internal and external lubricating effect into the PA engineering plastic.
The specific implementation mode is as follows:
in order to better understand the present invention, the following examples further illustrate the invention, the examples are only used for explaining the invention, not to constitute any limitation of the invention.
Pure PA system:
example 1
The lubricant comprises the following components in percentage by weight: the component A is high molecular weight fatty acid-adipic acid-pentaerythritol polymerization composite ester, the mass fraction of the component A accounts for 60% of the whole lubricant system, the structure is shown as a formula I, wherein the molar ratio of fatty acid to adipic acid to pentaerythritol is 2.05:1:0.46, and the fatty acid is stearic acid. The component B is formed by mixing calcium stearate and barium stearate according to the mass ratio of 1:1, wherein the mass fraction accounts for 20% of the whole lubricant system; the component C contains polar group-containing ultrahigh molecular weight polysiloxane, the structure is shown as a formula II, the mass fraction accounts for 15% of the whole lubricant system, wherein the polar group R is carbamido and accounts for 5% of the total number of side chains, and the viscosity average molecular weight is 30 ten thousand; the component D is precipitated white carbon black subjected to in-situ modification by a silane coupling agent, the mass fraction of the precipitated white carbon black accounts for 5% of the whole lubricant system, and the particle size of the precipitated white carbon black is 8 microns.
Preparation of the lubricant composition. And (3) stirring the precipitated silica modified by the component D and the polar group-containing ultrahigh molecular weight polysiloxane of the component C at normal temperature and high speed for 10min to form powder in a high-speed stirrer, and stirring and mixing the powder, the high molecular weight fatty acid-adipic acid-pentaerythritol polymer ester of the component A and the higher fatty acid salt of the component B at high speed and room temperature for 5min to form powder. The lubricant compositions in the following examples were prepared in accordance with this method.
And (3) preparing modified particles. 100 parts of PA6YH800 (Yueyangpetrochemical product, intrinsic viscosity 2.85, the same below) obtained after vacuum drying at 90 ℃ for 12 hours, 0.15 part of antioxidant 1098, 0.15 part of antioxidant 168 and 0.3 part of lubricant are uniformly mixed, melted, mixed, extruded and granulated at 235 ℃ in a double-screw extruder with the length-diameter ratio of 1:35, the extrusion speed is 260rmp, the feeding speed is 15rmp, and the current during stable extrusion is recorded to obtain the PA6 modified particles.
Example 2
The lubricant composition in example 2 was formulated as in example 1, with 0.5 part lubricant added, and the remaining preparation procedure was the same as in example 1.
Comparative example 1
The rest process proportion is the same as that of the example 1 without adding the lubricant.
Comparative example 2
The lubricant is pentaerythritol stearate (product of Lonza, USA, trade name of the product is
P, the same below), the addition amount is 0.5 part, and the rest process ratio is the same as that of the example 1.
Comparative example 3
The lubricant comprises the following components in percentage by weight: the component A is pentaerythritol stearate with the mass fraction of 60 percent; the component B is calcium stearate with the mass fraction of 20 percent; the component C is ultrahigh molecular weight polysiloxane with methyl side chains, the mass fraction is 15 percent, and the viscosity average molecular weight is 30 ten thousand; the component D is common precipitated silica, the mass fraction is 5%, the particle size is 8 μm, and the preparation process of the lubricant composition is the same as that in example 1.
The addition amount of the lubricant is 0.5 part, and the rest process proportion is the same as that of the example 1.
PA plus 30% glass fiber system:
example 3
The lubricant comprises the following components in percentage by weight: the component A is high-molecular-weight fatty acid-adipic acid-pentaerythritol polymerization composite ester, the mass fraction of the component A accounts for 50% of the whole lubricant system, and the structure of the component A is shown as a formula I, wherein the molar ratio of fatty acid to adipic acid to pentaerythritol is 2.05:1:0.48, and the fatty acid is stearic acid. The component B is formed by mixing calcium stearate and zinc stearate according to the mass ratio of 2:1, wherein the mass fraction accounts for 25% of the whole lubricant system; the component C contains polar group-containing ultrahigh molecular weight polysiloxane, the structure is shown as a formula II, the mass fraction accounts for 15% of the whole lubricant system, wherein the polar group R is carbamido and accounts for 5% of the total number of side chains, and the viscosity average molecular weight is 30 ten thousand; the component D is white carbon black subjected to in-situ modification by a silane coupling agent, the mass fraction of the white carbon black accounts for 10% of the whole lubricant system, the particle size is 8 mu m, and the preparation process of the lubricant composition is the same as that of the lubricant composition in example 1.
And (3) preparing modified particles. Uniformly mixing 70 parts of PA6YH800 subjected to vacuum drying at 90 ℃ for 12h, 30 parts of boulder chopped glass fiber 560A, 0.15 part of antioxidant 1098, 0.15 part of antioxidant 168 and 0.3 part of lubricant, performing melt mixing extrusion granulation at 250 ℃ in a double-screw extruder with the length-diameter ratio of 1:35 at an extrusion speed of 280rmp and a feeding speed of 15rmp, and recording the current during stable extrusion to obtain the modified particles of the PA engineering plastic.
Example 4
The lubricant ratio in example 4 is the same as that in example 3, wherein the lubricant is added in 0.5 part, and the rest process ratios are the same.
Comparative example 4
The rest process proportion is the same as that of the example 3 without adding the lubricant.
Comparative example 5
The lubricant is pentaerythritol stearate with the addition amount of 0.5 part, and the rest process proportion is the same as that of the example 3.
Comparative example 6
The lubricant comprises the following components in percentage by weight: the component A is pentaerythritol stearate with the mass fraction of 50 percent; the component B is calcium stearate with the mass fraction of 25 percent; the component C is ultrahigh molecular weight polysiloxane with methyl side chains, the mass fraction is 15 percent, and the viscosity average molecular weight is 30 ten thousand; the component D is common precipitated white carbon black with the mass fraction of 10 percent and the particle size of 8 mu m.
The addition amount of the lubricant is 0.5 part, and the rest process proportion is the same as that of the example 3.
PA plus 30% talc system:
example 5
The lubricant composition comprises the following components in percentage by weight: the component A is high molecular weight fatty acid-adipic acid-pentaerythritol polymerization composite ester, the mass fraction of the component A accounts for 60% of the whole lubricant system, the structure is shown as a formula I, wherein the molar ratio of fatty acid to adipic acid to pentaerythritol is 2.05:1:0.48, and the fatty acid is stearic acid. The component B is formed by mixing calcium stearate and zinc stearate according to the mass ratio of 1:1, wherein the mass fraction accounts for 25% of the whole lubricant system; the component C contains polar group-containing ultrahigh molecular weight polysiloxane, the mass fraction of which accounts for 10 percent of the whole lubricant system, and the structure is shown as a formula II, wherein the polar group R is carbamido and accounts for 5 percent of the total number of side chains, and the viscosity average molecular weight is 30 ten thousand; the component D is white carbon black in-situ modified by a silane coupling agent, the mass fraction of the white carbon black accounts for 5% of the whole lubricant system, the particle size is 8 mu m, and the preparation process of the lubricant composition is the same as that of the lubricant composition in example 1.
And (3) preparing modified particles. Uniformly mixing 70 parts of PA6YH800 subjected to vacuum drying at 90 ℃ for 12h, 30 parts of 1500-mesh talcum powder, 0.15 part of antioxidant 1098, 0.15 part of antioxidant 168 and 0.3 part of lubricant, performing melt mixing extrusion granulation at 250 ℃ in a double-screw extruder with the length-diameter ratio of 1:35, wherein the extrusion speed is 280rmp, the feeding speed is 15rmp, and recording the current during stable extrusion to obtain the modified PA engineering plastic particles.
Example 6
The lubricant composition in example 6 was prepared in the same manner as in example 5, except that the amount of the lubricant was 0.5 part.
Comparative example 7
The rest process proportion is the same as that of the example 5 without adding the lubricant.
Comparative example 8
The lubricant is pentaerythritol stearate with the addition amount of 0.5 part, and the rest process proportion is the same as that of the example 5.
Comparative example 9
The lubricant comprises the following components in percentage by weight: the component A is pentaerythritol stearate with the mass fraction of 60 percent; the component B is calcium stearate with the mass fraction of 25 percent; the component C is ultrahigh molecular weight polysiloxane with methyl side chains, the mass fraction is 10 percent, and the viscosity average molecular weight is 30 ten thousand; the component D is common precipitated white carbon black, the mass fraction is 5%, and the particle size is 8 mu m.
The addition amount of the lubricant is 0.5 part, and the rest process proportion is the same as that of the example 5.
The amounts of the respective components in the above examples and comparative examples are combined as shown in Table 1:
TABLE 1
The modified particles granulated in the above examples and comparative examples are dried in a vacuum oven at 90-100 ℃ for 4 hours, and then the dried particle materials are injection molded on an injection molding machine according to the dimensions of ISO527-2(1996), ISO178-2003 and ISO179-2000 standards to prepare mechanical property test bars for property testing.
Melt index test: the melt flow rate test was carried out according to ISO1133-2005 at 260 ℃ X2.16 Kg.
And (3) testing mechanical properties: tensile properties were measured according to ISO527-2(1996) with specimen dimensions 170X 10X 4mm and a tensile speed of 50 mm/min; the bending property test is carried out according to ISO178-2003, the size of a sample is 80 multiplied by 10 multiplied by 4mm, the bending speed is 2mm/min, and the span is 64 mm; the impact strength of the notch of the simply supported beam is carried out according to ISO179-2000, the size of a test sample is 80 multiplied by 6 multiplied by 4mm, and the depth of the notch is one third of the thickness of the test sample.
And (3) torque testing: a Harper RM-200A torque rheometer is adopted for torque testing, and the torque testing parameters of a pure PA system are as follows: the temperature of the I zone is 235 ℃, the temperature of the II zone is 235 ℃, the temperature of the III zone is 235 ℃, the rotor is a plastic rotor, the rotating speed is 60rmp, the addition amount of particles is 50g, and the value when the torque is stable is the balance torque. The torque test parameters of the system of PA plus 30% glass fiber and PA plus 30% talcum powder are as follows: the temperature of the I area is 260 ℃, the temperature of the II area is 260 ℃, the temperature of the III area is 260 ℃, the rotor is a plastic rotor, the rotating speed is 60rmp, the addition amount of particles is 50g, and the value when the torque is stable is the balance torque.
And (3) testing the demolding force: the ejection force was determined by preparing a rectangular molded article with reinforcing ribs using an injection molding method and recording the force required of the ejector for the ejection process. The melt temperatures of example 1 and comparative example 1 were 235 ℃ and the melt temperatures of example 2, example 3, example 4, example 5, example 6, comparative example 2 and comparative example 3 were 260 ℃ when the thermoplastic molding compositions were injected into the molds (at the mold). The mold temperature was controlled at 80 ℃. The pressure was maintained at 350 bar for 8 seconds, and the molded article was cooled for 20 seconds and then demolded. The stripping process uses 12 stripper pins that are simultaneously pneumatically moved by means of a metal plate. The force required to urge the 12 ejector pins against the molded article and thus eject the molded article is recorded electronically by means of a force sensor, the highest force occurring being regarded as the ejection force.
The above test results are shown in table 2:
TABLE 2
From the test results, compared with the pure PA system without adding a lubricant, the composition with the internal and external lubricating effect improves the fluidity of the system by more than 20 percent, greatly reduces the demolding force, and basically has no influence on the mechanical property; compared with the lubricant added with pentaerythritol stearate, the composition with the internal and external lubricating effect improves the system fluidity by more than 15 percent, obviously improves the demolding effect and basically has no influence on the mechanical property; compared with the lubricant composition prepared from common polysiloxane without polar groups and non-modified white carbon black, the lubricant composition has greatly improved influence on mechanical properties.
In a PA6+ 30% chopped glass fiber system, compared with a system without adding a lubricant, the composition with the internal and external lubricating effect improves the fluidity of the system by more than 30%, greatly reduces the demolding force and has a slightly improved effect on the mechanical property; compared with the lubricant added with pentaerythritol stearate, the composition with the internal and external lubricating effect improves the system fluidity by more than 20 percent, obviously improves the demolding effect and has no influence on the mechanical property; compared with the lubricant composition prepared from common polysiloxane without polar groups and non-modified white carbon black, the mechanical property is greatly improved.
In a PA6+ 30% talcum powder system, compared with a system without adding a lubricant, the composition with the internal and external lubricating effect improves the fluidity of the system by more than 25%, greatly reduces the demolding force, and basically has no influence on the mechanical property; compared with the lubricant added with pentaerythritol stearate, the composition with the internal and external lubricating effect improves the system fluidity by more than 15 percent, obviously improves the demolding effect and basically has no influence on the mechanical property; compared with the lubricant composition prepared from common polysiloxane without polar groups and non-modified white carbon black, the lubricant composition has greatly improved influence on mechanical properties.
Claims (6)
1. A composition with internal and external lubrication functions for PA engineering plastics is characterized by comprising the following components in percentage by mass:
and (2) component A: 40-80% of high molecular weight fatty acid-adipic acid-pentaerythritol polymerized composite ester;
and (B) component: 10-30% of higher fatty acid salt;
and (3) component C: polar group-containing ultrahigh molecular weight polysiloxane 10-30%;
and (3) component D: 2-15% of modified white carbon black;
the sum of the mass percentages of the components is 100 percent;
wherein the structure of the polar group-containing ultrahigh molecular weight polysiloxane is shown as a formula II and is a block copolymer of … AAAAA-BBBBBB-AAA-BBBB …,
the viscosity-average molecular weight of the ultra-high molecular weight polysiloxane is between 20 and 50 ten thousand; the side chain group R of the ultrahigh molecular weight polysiloxane is one of carbamido, cyano, epoxy quaternary ammonium salt group, amino, carboxyl and hydroxyl; the number of the polar groups R of the side chain of the ultra-high molecular weight polysiloxane accounts for more than 2 percent of the total number of the side chain groups.
2. The composition for PA engineering plastics with internal and external lubrication functions as claimed in claim 1, wherein the high molecular fatty acid-adipic acid-pentaerythritol polymeric ester is prepared by reacting fatty acid, adipic acid and pentaerythritol to obtain a product with a structure shown as formula I:
wherein R is C10-C30N is a natural number of 1 to 30.
3. The composition for PA engineering plastics with internal and external lubrication functions as claimed in claim 2, wherein the molar ratio of fatty acid to adipic acid to pentaerythritol is 2-2.2:1: 0.45-0.495.
4. The composition for PA engineering plastics with internal and external lubrication functions as claimed in claim 1, wherein the higher fatty acid salt is: one or a mixture of more of lithium stearate, sodium stearate, potassium stearate, magnesium stearate, calcium stearate, barium stearate, aluminum stearate and zinc stearate.
5. The composition with internal and external lubricating functions for PA engineering plastics according to claim 1, wherein the particle size of the modified white carbon black is in the range of 10nm-100 μm.
6. The composition with internal and external lubrication effects for PA engineering plastics according to claim 1, wherein the modified white carbon black is one or a mixture of more of organochlorosilane modified white carbon black, siloxane modified white carbon black, silane coupling agent modified white carbon black and alcohol ester modified white carbon black.
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| US5916939A (en) * | 1994-02-25 | 1999-06-29 | Imperial Chemical Industries Plc | Internal mold release compositions |
| CN1037275C (en) * | 1994-11-11 | 1998-02-04 | 西安近代化学研究所 | External lubricating agent for polyvinyl-chloride use |
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Denomination of invention: A composition with internal and external lubrication effect for PA engineering plastics Effective date of registration: 20231009 Granted publication date: 20200317 Pledgee: Bank of China Limited Shangyu sub branch Pledgor: ZHEJIANG JAVA SPECIALTY CHEMICALS Co.,Ltd. Registration number: Y2023980060206 |
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