CN111592746A - Ceramic white filled laser-engravable polycarbonate compound and preparation method thereof - Google Patents

Ceramic white filled laser-engravable polycarbonate compound and preparation method thereof Download PDF

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CN111592746A
CN111592746A CN202010373325.XA CN202010373325A CN111592746A CN 111592746 A CN111592746 A CN 111592746A CN 202010373325 A CN202010373325 A CN 202010373325A CN 111592746 A CN111592746 A CN 111592746A
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parts
antioxidant
powder
polycarbonate compound
laser
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CN111592746B (en
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应杰
邱琪浩
顾亥楠
张豪杰
周浩
罗锐
章兴
施懿军
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Ningbo Zhetie Daphoon Chemical Co ltd
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    • C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
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    • C08J2479/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2461/00 - C08J2477/00
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K5/00—Use of organic ingredients
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    • C08K5/00—Use of organic ingredients
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Abstract

The invention relates to the technical field of modification of thermoplastic high polymer materials, and discloses a ceramic white filled laser carving polycarbonate compound which comprises the following components in parts by weight: 100 parts of PC particles and PC powder; 2-8 parts of polyester; 4-20 parts of inorganic filler; 6-10 parts of titanium dioxide; 0.1-0.7 part of ester exchange inhibitor; 0.1-0.4 part of sulfonate; 0.2-0.5 part of end-capping agent; 2-5 parts of laser carving master batch; 0.3-1 part of other auxiliary agents; 5-6 parts of silicone oil. The invention has the following advantages and effects: the ester exchange reaction of the PC particles, the PC powder and the polyester reduces the internal stress of the compound; the inorganic filler improves the strength; the addition of the sulfonate and the end-capping reagent solves the problem that the thermal stability is reduced due to excessive hydroxyl end groups caused by an ester exchange method; the cost is reduced by self-making the laser etching master batch, and the problem of poor laser etching effect caused by uneven dispersion due to the addition of a small amount of laser etching powder is solved by adopting the laser etching master batch, so that the ceramic white filling laser etching polycarbonate compound with low internal stress, high strength, good dimensional stability and high thermal stability is obtained.

Description

Ceramic white filled laser-engravable polycarbonate compound and preparation method thereof
Technical Field
The invention relates to the technical field of modification of thermoplastic high polymer materials, in particular to a ceramic white filled laser carving polycarbonate compound and a preparation method thereof.
Background
Marks for identification such as trademarks, bar codes and numbers on traditional transparent PC plastic products are usually generated by external processing modes such as printing, label sticking, hot stamping and shrinking outer packages, or by directly machining the surfaces of the plastic products, such as stamping, carving, punching and the like to form marks. However, the identification on the merchandise becomes blurred and incomplete due to mechanical damage, friction and the like during the storage and transportation of the merchandise, so that the identification is not clear; even after the article is used for a period of time, the marks on the surface of the article are worn away or faded away, which makes identification difficult.
Laser marking is a technique that uses the thermal effect of a laser to ablate the surface material of an object leaving a permanent mark. Compared with the traditional marking methods such as electrochemistry, machinery and the like, the method has the advantages of no pollution, high speed, high quality, high flexibility, no contact with a working surface and the like.
At present, a patent with publication number CN108410149A discloses a halogen-free flame-retardant high-gloss porcelain white polycarbonate composite material, which comprises the following raw materials in parts by weight: 85-95 parts of polycarbonate, 0.4-1 part of halogen-free flame retardant, 1-5 parts of toughening agent, 0.5-1 part of antioxidant, 0.2-0.6 part of flow agent and 2-8 parts of titanium dioxide. The toughening agent is compounded with the high-fluidity halogen-free flame retardant and the flowing agent, so that the melt fluidity is good, the molding efficiency and the surface gloss are high, and the mechanical property, the flame retardance and the electrical property are excellent.
The above prior art solutions have the following drawbacks: the prior polycarbonate has poor thermal stability, is easy to carbonize or bubble when being applied to laser marking and is marked by laser, forms dark or light-colored marks on the surface and easily causes the problem of poor marking effect.
Disclosure of Invention
Aiming at the defects in the prior art, the first purpose of the invention is to provide a ceramic white filled laser-engravable polycarbonate compound which has better thermal stability and can achieve better laser-engraving effect.
In order to achieve the purpose, the invention provides the following technical scheme:
the ceramic white filled laser-engravable polycarbonate compound comprises the following components in parts by weight:
Figure BDA0002478964600000011
Figure BDA0002478964600000021
by adopting the technical scheme, the mixing of the PC particles and the PC powder can reduce the using amount of the PC powder and improve the uniform mixing degree between the PC and the components; a small amount of polyester is added into the PC particles and the PC powder, and the internal stress of the polycarbonate is reduced through ester exchange reaction; meanwhile, the cost of the polycarbonate is reduced by adding the inorganic filler, the strength and the modulus of the polycarbonate are improved, and the shrinkage rate of the compound is reduced; by adding the sulfonate and the end-capping reagent, excessive hydroxyl end groups of the polycarbonate caused by the ester exchange method are reduced, and the problem of the reduction of the overall thermal stability of the polycarbonate caused by excessive hydroxyl end groups is solved; adopt self-control radium carving master batch, compare with the radium carving powder that adopts commercially available, on the one hand laser marking effect is equivalent but cost reduction, on the other hand, when adding a small amount of radium carving powder alone, make the uneven relatively poor problem that arouses the radium carving effect of dispersion because of the powder addition is less easily, this problem has been solved in the use of radium carving master batch, but radium carving polycarbonate complex is filled to the porcelain white that obtains from this, but has the internal stress low, intensity is high, dimensional stability is good, and moderate advantage of cost, especially, possess better heat stability, can reach better radium carving effect.
The present invention in a preferred example may be further configured to: the adhesive also comprises 2-3 parts of 1, 2-dichloroethane, 10-15 parts of polyethylene diamine and 4-6 parts of terephthaloyl chloride according to parts by weight.
By adopting the technical scheme, the thermal stability of the material can be improved by polymer crosslinking between the polycarbonate and the polyethylene diamine, and more bonds must be broken in the same chain segment to show weight loss or mechanical strength reduction; the poly (ethylene diamine) is a three-dimensional agglomerate and has high regularity and symmetry, a stronger reticular structure is formed by crosslinking, the structural strength of the polycarbonate compound can be effectively enhanced, and the aim of improving the thermal stability is further fulfilled; the mixture containing the amido can form hydrogen bonds between molecules, and the intermolecular force is enhanced, so that the thermal stability of the polycarbonate compound is improved.
The present invention in a preferred example may be further configured to: the adhesive also comprises 1 to 2 parts of trimellitate and 0.4 to 0.6 part of triethanolamine according to parts by weight.
By adopting the technical scheme, on one hand, the addition of the trimellitate can reduce the generation speed of free radicals, so that the thermal decomposition of the polycarbonate is inhibited, and the thermal stability of the polycarbonate compound is further improved; on the other hand, the amino group contained in triethanolamine can deactivate unstable unsaturated groups in trimellitate, thereby improving the stability of the components and thus assisting in improving the thermal stability of the mixture of trimellitate and polycarbonate.
The present invention in a preferred example may be further configured to: according to the weight portion, the product also comprises 8-10 portions of isobutyl acetate.
By adopting the technical scheme, the addition of the isobutyl acetate has certain effects of improving the interfacial associativity among the components and improving the compatibility of each component; meanwhile, the addition of the isobutyl acetate can generate better synergistic effect with triethanolamine, thereby synergistically improving the chain segment distribution of the compound, improving the compatibility among all components and being beneficial to increasing the thermal stability of the polycarbonate compound.
The present invention in a preferred example may be further configured to: the laser etching master batch comprises the following components in percentage by weight: 86-90% of PC powder, 4-6% of antimony trioxide, 0.2-0.4% of bismuth oxide, 2-4% of silicon dioxide, 0.5-1% of tin dioxide, 1-2% of antioxidant and 1-2% of mold release agent; the laser etching master batch is 3 parts by weight.
By adopting the technical scheme, the laser carving master batch is obtained by self-making according to the proportion, and compared with commercially available laser carving powder, the self-made laser carving master batch has the advantages that the laser marking effect is equivalent, but the cost is reduced, and the price advantage is brought to the product; meanwhile, the laser etching master batch is prepared, so that the problem of poor laser etching effect caused by less powder addition amount and uneven dispersion easily caused by adding a small amount of laser etching powder independently is solved; experiments prove that when the laser etching master batch is 3 parts, the laser etching effect is optimal, the laser etching effect of the laser etching master batch is continuously increased and is not changed, and when the cost is considered, the addition amount of the laser etching master batch is optimal when the addition amount is 3 parts.
The present invention in a preferred example may be further configured to: the polyester is at least one of polybutylene terephthalate and polyethylene terephthalate, and the viscosity is 0.8-0.9 dL/g; the ester exchange inhibitor is one of alkyl phosphate ester exchange inhibitor and anhydrous sodium dihydrogen phosphate.
By adopting the technical scheme, the polycarbonate has high integral rigidity due to the benzene ring contained in the molecular chain, so that the melt has high viscosity and poor fluidity, the internal stress residue is large in the process of injection molding of a PC (polycarbonate) into a product, the stress cannot be released, the product is easy to crack, and the PC is sensitive to a notch, so that a small amount of polyester is added into the PC to reduce the stress residue through partial ester exchange; while excessive transesterification tends to result in a decrease in rigidity of PC, resulting in a decrease in strength and modulus, the addition of a small amount of a transesterification inhibitor reduces the transesterification reaction between PC and polyester.
The present invention in a preferred example may be further configured to: the sulfonate is one of potassium perfluorobutyl sulfonate and diphenyl sulfone sulfonate; the end-capping agent is a low molecular weight prepolymer with epoxy groups at the head and tail ends of a molecular chain or a block copolymer with a plurality of epoxy groups on a branched chain; the inorganic filler is a compound of barium sulfate and talcum powder; the titanium dioxide is special for PC.
By adopting the technical scheme, on one hand, the addition of the sulfonate is beneficial to improving the glow wire temperature of the polycarbonate compound and meeting the laser etching requirement of the polycarbonate compound, and on the other hand, the problem that the thermal stability of the polycarbonate whole body is reduced easily due to excessive hydroxyl at the polycarbonate end in the ester exchange method is solved by adding the sulfonate and the end-capping reagent; the inorganic filler has the advantages of low price and improvement on the dimensional stability of the product, can reduce the cost and increase the strength of the polycarbonate when added into the polycarbonate, and can reduce the dimensional shrinkage phenomenon of an injection molding product in the die sinking process, reduce the manufacturing period of a finished product and improve the production efficiency.
The present invention in a preferred example may be further configured to: the other auxiliary agent is at least one of an antioxidant, a release agent and an ultraviolet absorbent; wherein the antioxidant comprises one of antioxidant 1010, antioxidant 168, antioxidant 626, antioxidant 1076, antioxidant S-9228 and antioxidant 412S; the release agent comprises one of polyethylene wax, paraffin, ethylene bis-stearic acid amide and pentaerythritol bis-stearate; the ultraviolet absorbent comprises one of UV-329, UV-234, UV-360, UV-1577 and UV-1164.
By adopting the technical scheme, at least one of an antioxidant, a release agent and an ultraviolet absorbent is added to assist in improving the overall performance of the polycarbonate compound, so that the ceramic white polycarbonate compound which is low in internal stress, high in strength, good in size stability, high in thermal stability and good in laser etching effect is obtained.
The second purpose of the invention is to provide a preparation method of the ceramic white filled laser-engravable polycarbonate compound.
In order to achieve the second object, the invention provides the following technical scheme:
a preparation method of ceramic white filled laser carving polycarbonate compound comprises the following steps:
s1, laser etching master batch: weighing PC powder, an antioxidant, a release agent, antimony trioxide, bismuth oxide, silicon dioxide, tin dioxide and other materials in proportion, putting the materials into a powder grinding machine, and adding silicone oil to uniformly mix the materials; then placing the uniformly mixed material in a double-screw extruder with the rotating speed of 200-;
s2, weighing PC particles, PC powder, polyester, inorganic filler, titanium dioxide, ester exchange inhibitor, sulfonate, end-capping agent, radium carving master batch, other auxiliary agents and the like according to a formula ratio, adding into a high-speed mixer, and stirring for 5-10 minutes; then putting the mixed raw materials into a double-screw extruder for extrusion granulation, wherein the length-diameter ratio of screws is 32-36:1, the temperature of each section of screw is 240-280 ℃; the temperature of the feeding section in the double-screw extruder is 200-.
By adopting the technical scheme, the ceramic white polycarbonate compound with low internal stress, high strength, good dimensional stability and higher thermal stability is prepared.
The present invention in a preferred example may be further configured to: in the S2, after the raw materials are mixed, polyethylene diamine can be added, and the mixture is stirred and reacted for 10 to 15 minutes at the temperature of between 60 and 70 ℃; then adding 1, 2-dichloroethane, terephthaloyl chloride and trimellitate, adjusting the temperature to 40-50 ℃, and stirring for 5-10 minutes to obtain a mixture; when the mixture is cooled to room temperature, adding triethanolamine and isobutyl acetate, and stirring for 4-5 minutes.
By adopting the technical scheme, the ceramic white polycarbonate compound which has low internal stress, high strength, good dimensional stability, high thermal stability and better laser etching effect can be further prepared.
In summary, the invention includes at least one of the following beneficial technical effects:
the mixing of the PC particles and the PC powder can reduce the dosage of the PC powder and improve the uniform mixing degree between the PC and the components; a small amount of polyester is added into the PC particles and the PC powder, and the internal stress of the polycarbonate is reduced through ester exchange reaction; the inorganic filler improves the strength of the polycarbonate; the addition of the sulfonate and the end-capping reagent solves the problem that the thermal stability is reduced due to excessive hydroxyl end groups caused by an ester exchange method; the cost is reduced by self-preparing the laser etching master batch, and the problem of poor laser etching effect caused by uneven dispersion due to the addition of a small amount of laser etching powder is solved by adopting the laser etching master batch, so that the ceramic white filling laser etching polycarbonate compound with low internal stress, high strength, good dimensional stability and good thermal stability is obtained;
2. polymer cross-linking between polycarbonate and polyethylene diamine can improve the thermal stability of the material, and more bonds must be broken in the same segment to show weight loss or mechanical strength reduction; the polyethylene diamine has high regularity and symmetry, a stronger reticular structure is formed by crosslinking, the structural strength of the polycarbonate compound can be effectively enhanced, and then the aim of improving the thermal stability is achieved; the mixture containing the amide group can form hydrogen bonds among molecules, and the intermolecular force is enhanced, so that the thermal stability of the polycarbonate compound is improved;
3. the addition of trimellitate can reduce the generation speed of free radicals, thereby inhibiting the thermal decomposition of polycarbonate; the amino group contained in triethanolamine can inactivate an unstable unsaturated group in trimellitate, and the addition of isobutyl acetate has the effects of improving the interfacial associativity among components to a certain extent and improving the compatibility of each component; meanwhile, the addition of isobutyl acetate can generate a synergistic effect with triethanolamine, improve the chain segment distribution of the compound, and improve the compatibility among the components, thereby increasing the thermal stability of the polycarbonate compound.
Detailed Description
The present invention will be described in further detail below.
The embodiment of the invention adopts the following raw materials:
PC particles are PC02-20 produced by Zhejiang iron galenical chemical industry Co., Ltd, and MFR of the PC particles is 20g/10 min; the PC powder is prepared from FN1700 with MFR of 30g/10 min.
Polyester (PET) is BG-85 of China petrochemical certified chemical fiber GmbH, which is a highly viscous polyethylene terephthalate with an intrinsic viscosity of 0.879 dL/g.
BaSO4Barium sulfate, Guangzhou Macro mining science and technology, Inc., 3000 mesh.
Talc, Quanzhou Xufeng powder materials Limited, model BHS-8860, 3.4 um.
TiO2Rutile titanium dioxide, DuPont, USA, model R103.
NaH2PO4Anhydrous sodium dihydrogen phosphate, ester exchange inhibitor, national drug group chemical reagent limited.
KSS, a sulfonate flame retardant, a believed high molecular weight Co., Ltd., model FR235, with an effective content of 99%.
Epoxy blocking agent: CE-33, Kunshanding chemical Co., Ltd.
Sb2O3Antimony trioxide, Hongtai-based flame retardant materials Limited, Dongguan, with an effective content of not less than 99.8% and a theoretical antimony content of 83.54%.
Bi2O3Bismuth oxide, Chengdu alpha metal materials, Inc., with an effective content of > 99.99%.
SiO2The nano silicon dioxide is MG-SiO2-15, the model is Shanghai Moghai Moguo nanotechnology Co., Ltd, and the purity is 99.9%.
SnO2Tin dioxide, Zhengzhou Shangqi GmbH, the effective content is more than 99%.
The polyethylene diamine is synthesized from ethylene diamine, and antioxidant 1010, polyethylene wax, UV-1577, cornus 2233, Shiyuan PC-3, and other raw materials are all commercially available.
FT-IR spectrum analysis was performed on the polycarbonate composite to which polyethylene diamine and terephthaloyl chloride were added at 3425cm-1The reaction was observed to give an amide group by the N-H stretching vibration absorption peak of the amide group.
In the invention, the inorganic filler can be at least one of talcum powder, barium sulfate, hydrotalcite, mica, kaolin and glass beads, and the particle size is 3000-6000 meshes; the titanium dioxide is one of cornus 2233, Shiyuan PC-3, Kemu R350 and DuPont R103.
Examples
Example 1
The invention discloses a ceramic white filled laser carving polycarbonate compound and a preparation method thereof, wherein the ceramic white filled laser carving polycarbonate compound comprises the following steps:
s1, laser etching master batch: weighing PC powder, an antioxidant, a release agent, antimony trioxide, bismuth oxide, silicon dioxide, tin dioxide and other materials in proportion, putting the materials into a powder grinding machine, and adding 5 parts of silicone oil to uniformly mix the materials; then placing the uniformly mixed material in a double-screw extruder with the rotating speed of 260r/min and the temperature of 250 ℃ for extrusion, and preparing laser carving master batches through water cooling, air drying and grain cutting;
s2, weighing PC particles, PC powder, polyester, inorganic filler, titanium dioxide, ester exchange inhibitor, sulfonate, end-capping agent, radium carving master batch, other auxiliary agents and the like according to a formula ratio, adding into a high-speed mixer, and stirring for 8 minutes; adding polyethylene diamine, and stirring and reacting for 12 minutes at the temperature of 64 ℃; then adding 1, 2-dichloroethane, terephthaloyl chloride and trimellitate, adjusting the temperature to 44 ℃, and stirring for reacting for 6 minutes to obtain a mixture; when the mixture is cooled to room temperature, adding triethanolamine and isobutyl acetate, and stirring for 5 minutes; then putting the mixed materials into a double-screw extruder for extrusion granulation, wherein the length-diameter ratio of a screw is 33:1, and the temperature of each section of the screw is 260 ℃; the temperature of a feeding section in the double-screw extruder is 210 ℃, the temperature of a melting section is 265 ℃, the temperature of a homogenizing section is 240 ℃, and the temperature of a machine head is 230 ℃.
In example 1, the inorganic filler was a composite of barium sulfate and talc, and the particle size was 4500 mesh; the titanium dioxide is DuPont R103; other adjuvants include a combination of antioxidant 1010 and polyethylene wax, with the amounts of each component being shown in table 1 below.
Example 2
The invention discloses a ceramic white filled laser carving polycarbonate compound and a preparation method thereof, wherein the ceramic white filled laser carving polycarbonate compound comprises the following steps:
s1, laser etching master batch: weighing PC powder, an antioxidant, a release agent, antimony trioxide, bismuth oxide, silicon dioxide, tin dioxide and other materials in proportion, putting the materials into a powder grinding machine, and adding 5 parts of silicone oil to uniformly mix the materials; then placing the uniformly mixed materials in a double-screw extruder with the rotating speed of 200r/min and the temperature of 200 ℃ for extrusion, and preparing laser carving master batches through water cooling, air drying and grain cutting;
s2, weighing PC particles, PC powder, polyester, inorganic filler, titanium dioxide, ester exchange inhibitor, sulfonate, end-capping agent, radium carving master batch, other auxiliary agents and the like according to a formula ratio, adding into a high-speed mixer, and stirring for 5 minutes; adding polyethylene diamine, and stirring and reacting for 10 minutes at the temperature of 60 ℃; then adding 1, 2-dichloroethane, terephthaloyl chloride and trimellitate, adjusting the temperature to 40 ℃, and stirring for 5 minutes to react to obtain a mixture; when the mixture is cooled to room temperature, adding triethanolamine and isobutyl acetate, and stirring for 4 minutes; then putting the mixed materials into a double-screw extruder for extrusion granulation, wherein the length-diameter ratio of a screw is 32: 1, the temperature of each section of screw is 240 ℃; the temperature of a feeding section in the double-screw extruder is 200 ℃, the temperature of a melting section is 260 ℃, the temperature of a homogenizing section is 230 ℃, and the temperature of a machine head is 220 ℃.
In example 2, the inorganic filler was barium sulfate, and the particle size was 3000 mesh; the titanium dioxide is cornus 2233; other adjuvants include antioxidant 1010 and UV-1577 in the amounts shown in Table 1 below.
Example 3
The invention discloses a ceramic white filled laser carving polycarbonate compound and a preparation method thereof, wherein the ceramic white filled laser carving polycarbonate compound comprises the following steps:
s1, laser etching master batch: weighing PC powder, an antioxidant, a release agent, antimony trioxide, bismuth oxide, silicon dioxide, tin dioxide and other materials in proportion, putting the materials into a powder grinding machine, and adding 6 parts of silicone oil to uniformly mix the materials; then placing the uniformly mixed material in a double-screw extruder with the rotating speed of 300r/min and the temperature of 270 ℃ for extrusion, and preparing laser carving master batches through water cooling, air drying and grain cutting;
s2, weighing PC particles, PC powder, polyester, inorganic filler, titanium dioxide, ester exchange inhibitor, sulfonate, end-capping agent, radium carving master batch, other auxiliary agents and the like according to a formula ratio, adding into a high-speed mixer, and stirring for 10 minutes; adding polyethylene diamine, and stirring and reacting for 15 minutes at the temperature of 70 ℃; then adding 1, 2-dichloroethane, terephthaloyl chloride and trimellitate, adjusting the temperature to 50 ℃, and stirring for reaction for 10 minutes to obtain a mixture; when the mixture is cooled to room temperature, adding triethanolamine and isobutyl acetate, and stirring for 5 minutes; then putting the mixed materials into a double-screw extruder for extrusion granulation, wherein the length-diameter ratio of a screw is 36:1, the temperature of each section of screw is 280 ℃; the temperature of a feeding section in the double-screw extruder is 220 ℃, the temperature of a melting section is 270 ℃, the temperature of a homogenizing section is 250 ℃, and the temperature of a machine head is 240 ℃.
In example 3, the inorganic filler was talc, and the particle size was 6000 mesh; the titanium dioxide is stone PC-3; other adjuvants include antioxidant 1010, polyethylene wax and UV-1577 in the amounts shown in Table 1 below.
Examples 4 to 9
The difference from example 1 is that the contents of each component are shown in table 1 below.
Comparative example 1
The difference from example 1 is that polyester was not added and the contents of the respective components are shown in the following Table 2-1.
Comparative example 2
The difference from example 1 is that the transesterification inhibitor was not added and the contents of the respective components are shown in the following Table 2-1.
Comparative example 3
The difference from the example 1 is that the content of each component is shown in the following table 2-1 without adding the laser etching master batch.
Comparative example 4
The difference from example 1 is that no sulfonate was added and the contents of each component are shown in the following Table 2-1.
Comparative example 5
The difference from example 1 is that no polyethylene diamine was added and the contents of the respective components are shown in the following tables 2 to 2.
Comparative example 6
The difference from example 1 is that polyethylene diamine was replaced with polyaniline and the contents of the respective components are shown in tables 2 to 2 below.
Comparative example 7
The difference from example 1 is that terephthaloyl chloride was replaced with dioctyl terephthalate, and the contents of the respective components are shown in the following tables 2 to 2.
Comparative example 8
The difference from example 1 is that trimellitate ester was replaced with citrate ester, and the contents of the respective components are shown in the following tables 2 to 2.
Comparative example 9
The difference from example 1 is that triethanolamine was replaced with dimethylformamide and the contents of the respective components are shown in the following tables 2 to 2.
Comparative example 10
The difference from example 1 is that isobutyl acetate is replaced by PP-g-MAH, the contents of the components being shown in tables 2-2 below.
TABLE 1 ingredient content Table for each example
Figure BDA0002478964600000091
TABLE 2-1 ingredient content Table for comparative examples 1-4
Figure BDA0002478964600000092
Figure BDA0002478964600000101
Tables 2-2 tables for contents of components of comparative examples 5-10
Figure BDA0002478964600000102
Performance test
(1) Melt Flow Rate (MFR), measured according to GB/T3682 standard, at 300 ℃/1.2 kg.
(2) Mechanical property test, tensile strength and elongation at break: testing according to GB/T1040 standard, with test speed of 50 mm/min; notched impact strength (izod): testing according to ISO 180 standard.
(3) Internal stress detection, namely soaking a finished product workpiece in glacial acetic acid at 25 ℃ for 2min, taking out, cleaning with clear water, naturally drying in the air, and observing the surface condition, wherein the degree of white frost on the surface is related to the internal stress, and the larger the internal stress is, the more white frost is, and the larger the internal stress is, cracks are generated; the magnitude of the internal stress is judged according to the magnitude of "+", and the more "+", the larger the internal stress.
(4) Judging the laser etching effect: judging the laser etching effect according to the definition of the laser etching pattern contour and the pattern depth under default parameters (the speed is 500mm/s, the frequency is 20KHZ and the power is 50%); judging the laser etching effect according to the star, wherein the more star, the better the laser etching effect.
(5) The glow wire temperature was tested on a 1.5mm plaque at 850 ℃ according to GB/T5169.12. If the test sample did not ignite, the material is judged to be stable.
(6) The combustion performance is tested according to UL-94-2006; and judging the flame retardant grade according to the combustion performance, wherein the flame retardant grade is gradually increased from HB, V-2 and V-1 to V-0.
(7) And (3) performing a weight loss test according to GB/T2951.7, wherein the weight loss is expressed by the percentage of the weight loss in the original weight, and the larger the weight loss rate is, the poorer the thermal stability is.
The test results are shown in Table 3, Table 4-1, and Table 4-2 below.
TABLE 3 results of the Performance test of the examples
Figure BDA0002478964600000111
TABLE 4-1 Performance test results for example 1 and comparative examples 1-4
Figure BDA0002478964600000112
Figure BDA0002478964600000121
Tables 4-2 results of the Performance test of example 1 and comparative examples 5-10
Figure BDA0002478964600000122
From the results of table 3, the following conclusions can be drawn:
1. the glow wire temperature of the product can be improved by adding the sulfonate, and when the addition amount of the sulfonate reaches 0.3 part, the glow wire temperature can pass 960 ℃/2 mm.
2. The self-made laser etching master batch is added, so that the effect of laser etching is obviously improved, and the laser etching effect is better along with the increase of the addition amount of the laser etching master batch. When the addition amount of the laser carving master batch is more than 3 parts, the laser carving effect is optimal; the laser etching effect of the laser etching master batch is continuously increased and is not changed, and the optimal laser etching master batch is added in 3 parts in consideration of the cost.
From the results of Table 4-1, the following conclusions can be drawn:
1. from the comparison of example 1 with comparative example 1, it is known that the addition of polyester contributes to the reduction of the internal stress of the polycarbonate compound, since the slight transesterification of polyester with polycarbonate favors the movement of the molecular chains.
2. From example 1 compared to comparative example 2, no significant change in the measured properties occurred, but the transesterification inhibitor was able to control the transesterification reaction between PC and polyester, thereby avoiding excessive transesterification leading to a decrease in the overall stiffness of the material.
3. Comparing the example 1 with the comparative example 3, it can be known that the self-made laser etching master batch has better effect, and the laser etching pattern is clear and has better outline after the laser etching master batch is added.
4. Comparing example 1 with comparative example 4, it is known that the addition of sulfonate helps to increase the temperature and thermal stability of the glow wire and helps to improve the laser etching effect.
From the results of Table 4-2, the following conclusions can be drawn:
1. comparing example 1 with comparative example 5, it can be seen that the addition of polyethylene diamine helps to increase the temperature and thermal stability of the glow wire and helps to improve the laser etching effect.
2. Comparing example 1 with comparative examples 6-7, it is known that polyethylene diamine and terephthaloyl chloride have synergistic effect, and can improve the temperature and thermal stability of glow wire, so that the polycarbonate composite can achieve better laser etching effect.
3. From example 1 in comparison with comparative example 8, the addition of trimellitate had the effect of increasing glow wire temperature and thermal stability.
4. Comparing example 1 with comparative examples 8-9, it is known that trimellitate and triethanolamine have a synergistic effect, and the glow wire temperature and thermal stability can be improved, so that the polycarbonate compound can achieve a better laser etching effect.
5. From the comparison of example 1 with comparative examples 9-10, it is clear that the addition of isobutyl acetate has a certain effect on the improvement of thermal stability, since it can act synergistically with triethanolamine to improve the compatibility between the components.
The embodiments of the present invention are preferred embodiments of the present invention, and the scope of the present invention is not limited by these embodiments, so: all equivalent changes made according to the structure, shape and principle of the invention are covered by the protection scope of the invention.

Claims (10)

1. The utility model provides a but porcelain white fills radium carving polycarbonate compound which characterized in that: the composition comprises the following components in parts by weight:
PC particles and 100 parts of PC powder
2-8 parts of polyester
4-20 parts of inorganic filler
6-10 parts of titanium dioxide
0.1 to 0.7 portion of ester exchange inhibitor
0.1 to 0.4 portion of sulfonate
0.2 to 0.5 portion of end capping agent
2-5 parts of laser carving master batch
0.3 to 1 portion of other auxiliary agents
5-6 parts of silicone oil.
2. The porcelain white filled laser engravable polycarbonate compound according to claim 1, wherein: the adhesive also comprises 2-3 parts of 1, 2-dichloroethane, 10-15 parts of polyethylene diamine and 4-6 parts of terephthaloyl chloride according to parts by weight.
3. The porcelain white filled laser engravable polycarbonate compound according to claim 1, wherein: the adhesive also comprises 1-2 parts of trimellitate and 4-6 parts of triethanolamine according to parts by weight.
4. The porcelain white filled laser engravable polycarbonate compound according to claim 3, wherein: according to the weight portion, the product also comprises 8-10 portions of isobutyl acetate.
5. The porcelain white filled laser engravable polycarbonate compound according to claim 1, wherein: the laser etching master batch comprises the following components in percentage by weight: 86-90% of PC powder, 4-6% of antimony trioxide, 0.2-0.4% of bismuth oxide, 2-4% of silicon dioxide, 0.5-1% of tin dioxide, 1-2% of antioxidant and 1-2% of mold release agent; the laser etching master batch is 3 parts by weight.
6. The porcelain white filled laser engravable polycarbonate compound according to claim 1, wherein: the polyester is at least one of polybutylene terephthalate and polyethylene terephthalate, and the viscosity is 0.8-0.9 dL/g; the ester exchange inhibitor is one of alkyl phosphate ester exchange inhibitor and anhydrous sodium dihydrogen phosphate.
7. The porcelain white filled laser engravable polycarbonate compound according to claim 1, wherein: the sulfonate is one of potassium perfluorobutyl sulfonate and diphenyl sulfone sulfonate; the end-capping agent is a low molecular weight prepolymer with epoxy groups at the head and tail ends of a molecular chain or a block copolymer with a plurality of epoxy groups on a branched chain; the inorganic filler is a compound of barium sulfate and talcum powder; the titanium dioxide is special for PC.
8. The porcelain white filled laser engravable polycarbonate compound according to claim 1, wherein: the other auxiliary agent is at least one of an antioxidant, a release agent and an ultraviolet absorbent; wherein the antioxidant comprises one of antioxidant 1010, antioxidant 168, antioxidant 626, antioxidant 1076, antioxidant S-9228 and antioxidant 412S; the release agent comprises one of polyethylene wax, paraffin, ethylene bis-stearic acid amide and pentaerythritol bis-stearate; the ultraviolet absorbent comprises one of UV-329, UV-234, UV-360, UV-1577 and UV-1164.
9. The method for preparing porcelain white filled laser engravable polycarbonate compound according to any one of claims 1 to 8, wherein the method comprises the following steps: the method comprises the following steps:
s1, laser etching master batch: weighing PC powder, an antioxidant, a release agent, antimony trioxide, bismuth oxide, silicon dioxide, tin dioxide and other materials in proportion, putting the materials into a powder grinding machine, and adding silicone oil to uniformly mix the materials; then placing the uniformly mixed material in a double-screw extruder with the rotating speed of 200-;
s2, weighing PC particles, PC powder, polyester, inorganic filler, titanium dioxide, ester exchange inhibitor, sulfonate, end-capping agent, radium carving master batch, other auxiliary agents and the like according to a formula ratio, adding into a high-speed mixer, and stirring for 5-10 minutes; then putting the mixed raw materials into a double-screw extruder for extrusion granulation, wherein the length-diameter ratio of the screws is 32-36:1, and the temperature of each section of the screws is 240-; the temperature of the feeding section in the double-screw extruder is 200-.
10. The method for preparing a porcelain white filled laser-engravable polycarbonate compound according to claim 9, wherein the method comprises the following steps: in the S2, after the raw materials are mixed, polyethylene diamine can be added, and the mixture is stirred and reacted for 10 to 15 minutes at the temperature of between 60 and 70 ℃; then adding 1, 2-dichloroethane, terephthaloyl chloride and trimellitate, adjusting the temperature to 40-50 ℃, and stirring for 5-10 minutes to obtain a mixed material; when the mixed material is cooled to room temperature, adding triethanolamine and isobutyl acetate, and stirring for 4-5 minutes.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115746532A (en) * 2022-11-29 2023-03-07 金旸（厦门）新材料科技有限公司 Laser-engravable halogen-free flame-retardant reinforced polycarbonate material for relay and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090170985A1 (en) * 2007-12-28 2009-07-02 Rina Ai Polyester-polyamide compositions, articles, and method of manufacture thereof
JP2012041561A (en) * 2003-04-22 2012-03-01 Osaka Gas Co Ltd Fluorene-based composition and molded product of the same
CN103756277A (en) * 2013-12-30 2014-04-30 金发科技股份有限公司 Conductive polycarbonate composite, preparation method and application thereof
CN104031374A (en) * 2014-06-10 2014-09-10 惠州市沃特新材料有限公司 Polycarbonate composition and preparation method thereof
CN104672890A (en) * 2014-12-22 2015-06-03 杭州杭复新材料科技有限公司 Polymer matrix composite with laser-induced metallization characteristic
CN110267812A (en) * 2016-10-11 2019-09-20 沙特基础工业全球技术有限公司 Crystalline polycarbonate powder for the powder bed fusion in increasing material manufacturing

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012041561A (en) * 2003-04-22 2012-03-01 Osaka Gas Co Ltd Fluorene-based composition and molded product of the same
US20090170985A1 (en) * 2007-12-28 2009-07-02 Rina Ai Polyester-polyamide compositions, articles, and method of manufacture thereof
CN103756277A (en) * 2013-12-30 2014-04-30 金发科技股份有限公司 Conductive polycarbonate composite, preparation method and application thereof
CN104031374A (en) * 2014-06-10 2014-09-10 惠州市沃特新材料有限公司 Polycarbonate composition and preparation method thereof
CN104672890A (en) * 2014-12-22 2015-06-03 杭州杭复新材料科技有限公司 Polymer matrix composite with laser-induced metallization characteristic
CN110267812A (en) * 2016-10-11 2019-09-20 沙特基础工业全球技术有限公司 Crystalline polycarbonate powder for the powder bed fusion in increasing material manufacturing

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115746532A (en) * 2022-11-29 2023-03-07 金旸（厦门）新材料科技有限公司 Laser-engravable halogen-free flame-retardant reinforced polycarbonate material for relay and preparation method thereof

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