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CN113956642B - PC/PBT composition with high weld mark strength and preparation method thereof - Google Patents

PC/PBT composition with high weld mark strength and preparation method thereof Download PDF

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CN113956642B
CN113956642B CN202111260526.XA CN202111260526A CN113956642B CN 113956642 B CN113956642 B CN 113956642B CN 202111260526 A CN202111260526 A CN 202111260526A CN 113956642 B CN113956642 B CN 113956642B
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glycidol
diol
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CN113956642A (en
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陈晶斌
陈连清
祁先勇
张振威
童艳萍
齐鹏飞
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Wanhua Chemical Group Co Ltd
Wanhua Chemical Ningbo Co Ltd
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Wanhua Chemical Ningbo Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups

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Abstract

The invention provides a Polycarbonate (PC)/polybutylene terephthalate (PBT) composition with high weld mark strength and a preparation method thereof. By introducing the block copolymer, the glass transition temperature of the alloy (especially PC component) is reduced, so that the better molecular chain movement capability is kept when two melts meet, the mutual cohesiveness of the two melts is improved, and finally the weld mark strength is improved.

Description

PC/PBT composition with high weld mark strength and preparation method thereof
Technical Field
The invention belongs to the field of polymer materials, and particularly relates to a PC/PBT composition with high weld mark strength and a preparation method thereof.
Background
The PC/PBT alloy realizes good complementation of PC and PBT performances and has good comprehensive performances. On one hand, the PC improves the heat resistance and the impact resistance of the PBT; on the other hand PBT improves the chemical resistance of PC.
In relatively complex articles, weld marks are unavoidable. When two melts meet, the weld mark is a defect formed by the fact that the molecular chain movement capability is reduced due to the reduction of the temperature of the melts, and the mutual cohesiveness of the two melts is poor, and the weld mark is a mechanical weak point of a product and is easy to fail firstly under the action of external force. When the melt temperature is below the glass transition temperature of the polymer, the inter-melt adhesion is lost. The worse the mutual adhesion, the lower the weld line strength. The PC/PBT alloy is a composition and has a problem of low cost, which limits the wider application of the PC/PBT alloy. The improvement of the welding line strength of the alloy is mainly divided into two ways of forming process optimization and material optimization. The improvement of the molding process mainly comprises the improvement of injection molding temperature, mold temperature and the like. However, as the injection temperature and the mold temperature are increased, the risk of degradation of the material due to decomposition is also significantly increased. Material optimization is mainly to improve the compatibility of the alloy, i.e. by means of the addition of a compatibilising agent. However, the compatibilizing agent only partially improves the compatibility of the components and improves the interface effect, but the melt adhesion caused by the decrease of the melt temperature cannot be prevented, so that the effect of improving the weld mark strength of the compatibilizing agent is limited.
In summary, new methods are needed to further increase the weld line strength of PC/PBT.
Disclosure of Invention
The invention aims to provide a PC/PBT composition with high weld mark strength. The composition reduces the glass transition temperature of the alloy (especially the PC component), so that the two melts can keep better molecular chain movement capability when meeting, and further the mutual cohesiveness of the two melts is improved, and finally the weld mark strength is improved.
In order to achieve the above object, the present invention adopts the following technical scheme:
a high weld mark strength Polycarbonate (PC)/polybutylene terephthalate (PBT) composition comprising the following components: 30-70 parts by weight of PC;25-65 parts by mass of PBT;1 to 5 parts by weight of a block copolymer.
In the invention, the content of the terminal hydroxyl groups of the PC accounts for 10-30% of the terminal groups of the PC.
In the present invention, the melt flow index of PC is 3 to 65g/10min, preferably 7 to 50g/10min, when tested at 300℃under 1.2 kg.
In the present invention, the melt flow index of the PBT is 20 to 160g/10min, preferably 35 to 100g/10min, when tested at 240℃under 5 kg.
In the present invention, the block copolymer has the following structure:
Figure GDA0004199779420000021
wherein R is 1 、R 2 And R is 3 Having 3 to 8 carbon atomsAliphatic hydrocarbon groups and/or alkoxy groups of the children, R 1 、R 2 And R is 3 May be the same or different; m, n and k are integers more than or equal to 1; the number average molecular weight of the block copolymer is preferably 1000 to 7000.
In the invention, the preparation method of the block copolymer comprises the following steps:
s1: adding polycarbonate diol and double metal cyanide complex catalyst (DMC) into a reaction kettle to obtain a mixture a of the polycarbonate diol and DMC, introducing nitrogen to replace air, stirring, heating, and removing water in vacuum to obtain a mixture a' of the polycarbonate diol and DMC with low water content;
s2: heating the mixture a', adding part of glycidol to perform induction reaction, adding the rest of glycidol after the reaction is completed, and removing the rest of glycidol after the reaction is completed, thus obtaining the target block copolymer.
In the invention, the polycarbonate diol S1 is prepared by transesterification and polycondensation reaction of aliphatic diol and one or more of dimethyl carbonate, diethyl carbonate and diphenyl carbonate; preferably, the aliphatic diol is diol with carbon number not less than 3, preferably one or more of 1, 6-hexanediol, 1, 4-butanediol, 1, 3-butanediol, trimethylpentanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, dibromoneopentyl glycol, tetrabromodipentaerythritol, 2-methyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, triethylene glycol, 1, 4-dimethylolcyclohexane, cyclohexanediol, butylethylpropanediol, diethylpentanediol, ethylhexanediol, 1, 5-pentanediol and 1, 8-octanediol; more preferably one or more of 1, 6-hexanediol, 1, 4-butanediol, 1, 4-dimethylolcyclohexane, diethylene glycol, 1, 8-octanediol; preferably, the number average molecular weight of the polycarbonate diol is 500 to 3000, preferably 1000 to 2500.
In the invention, the DMC described in S1 is a powdery DMC catalyst taking tertiary butanol as one of ligands; preferably, the DMC catalyst as described in S1 is used in an amount of from 15 to 500ppm, preferably from 30 to 100ppm, based on the sum of the mass of polycarbonate diol and the mass of the total glycidol.
In the invention, the temperature of S1 is increased to 90-120 ℃.
In the present invention, the mixture a' in S1 has a water content of less than 0.05% by weight.
In the present invention, the molar ratio of the epoxypropanol to the polycarbonate diol as described in S2 is (3.5 to 75): 1, preferably (7 to 42): 1.
In the invention, the temperature of the a' of the S2 is raised to 100-160 ℃.
In the invention, 20% -80%, preferably 20% -60% of the total mass of the glycidol is added in the S2.
In the invention, optionally adding 0-5 parts of other auxiliary agents; preferably, the auxiliary agent is selected from one or more of flame retardants, toughening agents, compatibilizers, antioxidants, lubricants, ultraviolet absorbers, light stabilizers, heat stabilizers, metal deactivators, plasticizers, antiblocking agents, colorants, coupling agents, nucleating agents, foaming agents, antibacterial agents, mildewcides, acid scavengers, hydrolysis inhibitors, chain extenders, flow modifiers, matting agents, antistatic agents, reinforcing agents, fillers, antifogging agents, light diffusers, infrared absorbers, fluorescent brighteners and laser marking agents.
The compatibilizer is any one or combination of two or more of maleic anhydride grafted polyolefin (PO-MAH), maleic anhydride grafted hydrogenated styrene-butadiene block copolymer (SEBS-MAH), maleic anhydride grafted acrylonitrile-styrene-butadiene copolymer (ABS-MAH), styrene-maleic anhydride copolymer (SMA), styrene-maleic anhydride-acrylonitrile copolymer (SMAH), ethylene-methyl acrylate (EMA), ethylene-butyl acrylate (EBA) and ethylene-butyl acrylate-glycidyl methacrylate copolymer (PTW).
The antioxidant is one or the combination of two or more of hindered phenols, phosphites, thioesters, benzofurans, acrylyl modified phenols and hydroxylamine antioxidants.
The lubricant is one or the combination of two or more of fatty alcohols, metal soaps, fatty acids, fatty acid esters, montanic acid and derivatives thereof, amide waxes, saturated hydrocarbons, polyolefin waxes and derivatives thereof, organic silicon and silicone powders, organic fluorine and the like.
The ultraviolet absorbent is one or the combination of two or more of diphenyl ketone, benzotriazole, triazine, benzoate, cyanoacrylate and phenylimidazole.
The antistatic agent is one or a combination of two or more of distearyl hydroxylamine, triphenylamine, tri-N-octyl phosphine oxide, triphenylphosphine oxide, pyridine N-oxide and ethoxylated sorbitan monolaurate.
The PC/PBT composition with high weld mark strength can selectively use the auxiliary agent according to the performance characteristics of products, and achieves the purposes of improving the processability and the thermal oxidation aging resistance of the PC/PBT composition.
It is another object of the present invention to provide a process for preparing the high weld strength PC/PBT composition.
A method of making the high weld mark strength PC/PBT composition, the method comprising the steps of:
SS1: premixing: weighing and mixing PC, PBT, a block copolymer and optional auxiliary agents according to a proportion;
SS2: and (3) extruding: and extruding and granulating the mixture through a double-screw extruder to obtain the PC/PBT composition with high weld mark strength.
Further, in the preparation method, the temperature of a conveying section of the double-screw extruder is set to be 210-220 ℃, the temperature of a plasticizing section is set to be 225-250 ℃, the temperature of a metering section is set to be 225-245 ℃, the rotating speed of a screw is controlled to be 200-600rpm, and the vacuum degree of a vacuum pumping device of the double-screw metering section is controlled to be less than-0.7 bar.
Compared with the prior art, the invention has the following positive effects:
a block copolymer with a special structure is prepared by a synthetic method, and the addition of the block copolymer ensures that the composition (especially PC) maintains better molecular chain movement capability when two melts meet, so that the mutual cohesiveness of the two melts is better, and finally the weld mark strength is improved.
Detailed Description
The invention will be further described with reference to examples for a better understanding and implementation, but the invention is not limited to the examples listed and should also include any other known modifications within the scope of the claimed invention.
Preparation example 1
Raw materials for preparing polycarbonate diol (PCDL):
dimethyl carbonate: purity is more than or equal to 99 percent, and the production of the Ala-dine is carried out;
diethyl carbonate: purity is more than or equal to 99 percent, and the production of the Ala-dine is carried out;
diphenyl carbonate: purity is more than or equal to 99 percent, and the production of the Ala-dine is carried out;
1, 6-hexanediol: purity is more than or equal to 99 percent, and the production of the Ala-dine is carried out;
1, 4-butanediol: purity is more than or equal to 99 percent, and the production of the Ala-dine is carried out;
1, 4-bis-hydroxymethyl cyclohexane: purity is more than or equal to 99 percent, and the production of the Ala-dine is carried out;
diethylene glycol: purity is more than or equal to 99.5%, and the production of the Ala-dine is carried out;
1, 8-octanediol: purity is more than or equal to 98 percent, and the production of the Ala-dine is carried out;
the carbonic ester and the dihydric alcohol are metered into a reaction kettle according to a certain molar ratio in the proportion shown in the table 1, the total mass is 50g, tetrabutyl titanate with the dosage of 0.25 weight percent of the dihydric alcohol is added, and N is introduced 2 And (3) removing air in the reaction system for 2 hours, heating the reaction system under normal pressure to gradually raise the temperature of the reaction system to 120 ℃, and reacting for 2 hours. Then gradually increasing the temperature of the reaction system to 160 ℃ for reaction for 6 hours; and finally, the temperature of the system is increased to 180 ℃, the absolute pressure of the system is gradually reduced to 8kPa, the absolute pressure is kept to be 8KPa, the transesterification is carried out for 4 hours, and then the PCDL with certain relative molecular mass is obtained by cooling.
TABLE 1 Material ratios for PCDL preparation
Figure GDA0004199779420000071
Preparation example 2
Raw materials for preparing the block copolymer:
1. poly-1, 6-hexanediol carbonate, code PCDL-1 (self-made), moisture 0.05wt%, number average molecular weight 1002.
2. Poly-1, 4-butylene carbonate, code PCDL-2 (self-made), moisture 0.05wt%, number average molecular weight 504.
3. Poly-1, 4-bis (hydroxymethyl) cyclohexane carbonate, code PCDL-3 (homemade), moisture 0.05wt%, number average molecular weight 1986.
4. Poly (diethylene glycol carbonate), code PCDL-4 (homemade), moisture 0.05wt%, number average molecular weight 2899.
5. Poly-octyl/butylene carbonate, code PCDL-5, moisture 0.05wt%, number average molecular weight 2488.
6. Glycidol, GLD, shanghai Kaiser chemical Co.
7. The powdered double metal cyanide complex catalyst is named DMC, huaian Bade polyurethane science and technology Co.
Preparation of Block copolymer 1 (QD-1), comprising the steps of:
s1: 200g PCDL-1,0.0123g DMC was added to a pressure-resistant stainless steel reactor with a volume of 1L, nitrogen was substituted for air 2 times, stirring was started, heating to 90℃and vacuum removal of water under 10kPa pressure for 1h, and the water content was controlled to be lower than 0.05wt%.
S2: heating to 100deg.C, adding 53g of glycidol into the reaction kettle in the above step (1) for induction reaction, gradually dripping the rest 158g of glycidol after the induction reaction, removing unreacted glycidol after the reaction is completed to obtain block type oligomeric dihydric alcohol with the yield of 99%, measuring the hydroxyl value of 168.4mg KOH/g by phthalic anhydride-pyridine method (GB/T12008.3-2009), and the average molecular weight of 2008.
The structural formula of the product is as follows:
Figure GDA0004199779420000081
preparation of Block copolymer 2 (QD-2) the preparation method is:
s1: 200g PCDL-2 and 0.0404g DMC are added into a pressure-resistant stainless steel reaction kettle with the volume of 1L, air is replaced by nitrogen for 3 times, stirring is started, the temperature is heated to 110 ℃, the water is removed under vacuum under the pressure of 10kPa for 1h, and the water content is controlled to be lower than 0.03wt%.
S2: then heating to 120 ℃, adding 123.6g of epoxy propanol into the reaction kettle in the step (1) for induction reaction, gradually dripping the rest 82.4g of epoxy propanol after the induction reaction is finished, and removing unreacted epoxy propanol after the reaction is finished to obtain the segmented oligomeric dihydric alcohol with the yield of 99.1 percent, wherein the hydroxyl value is 129.4mgKOH/g and the average molecular weight is 1038 by the phthalic anhydride-pyridine method (GB/T12008.3-2009).
The structural formula of the product is as follows:
Figure GDA0004199779420000091
preparation of Block copolymer 3 (QD-3) the preparation method is:
s1: 150g PCDL-3 and 0.0572g DMC are added into a pressure-resistant stainless steel reaction kettle with the volume of 1L, nitrogen is used for replacing air for 2 times, stirring is started, the temperature is heated to 120 ℃, the water is removed in 10kPa for 1h in vacuum, and the water content is controlled to be lower than 0.02wt%.
S2: heating to 150 ℃, adding 84g of epoxy propanol into the reaction kettle in the step (1) to perform induction reaction, gradually dripping the rest 336g of epoxy propanol after the induction reaction is completed, and removing unreacted epoxy propanol after the reaction is completed to obtain the segmented oligomeric dihydric alcohol, wherein the yield is 98.1%, the hydroxyl value is 32.5mg KOH/g by a phthalic anhydride-pyridine method (GB/T12008.3-2009), and the average molecular weight is 6832.
Figure GDA0004199779420000101
Preparation of Block copolymer 4 (QD-4) the preparation method is:
s1: 200g PCDL-4 and 0.02508g DMC are added into a pressure-resistant stainless steel reaction kettle with the volume of 1L, air is replaced by nitrogen for 3 times, stirring is started, the temperature is heated to 120 ℃, water is removed in 10kPa for 1h, and the water content is controlled to be lower than 0.02wt%.
S2: heating to 160 ℃, adding 107g of epoxy propanol into the reaction kettle in the step (1) to perform induction reaction, gradually dripping the rest 107.5g of epoxy propanol after the induction reaction is completed, and removing unreacted epoxy propanol after the reaction is completed to obtain the polycarbonate-polyether glycol with the yield of 98.8%, wherein the hydroxyl value is 69.8mg KOH/g and the average molecular weight is 5937 by a phthalic anhydride-pyridine method (GB/T12008.3-2009).
The structural formula of the product is as follows:
Figure GDA0004199779420000102
preparation of Block copolymer 5 (QD-5) the preparation method is:
s1: 200g PCDL-5 and 0.00489g DMC are added into a pressure-resistant stainless steel reaction kettle with the volume of 1L, air is replaced by nitrogen for 1 time, stirring is started, the temperature is heated to 120 ℃, water is removed in 10kPa for 1h, and the water content is controlled to be lower than 0.02wt%.
S2: heating to 130 ℃, adding 100g of epoxy propanol into the reaction kettle in the step (1) to perform induction reaction, gradually dripping the rest 25g of epoxy propanol after the induction reaction is completed, and removing unreacted epoxy propanol after the reaction is completed to obtain the oligomeric dihydric alcohol, wherein the yield is 98.0%, the hydroxyl value is 68.7mg KOH/g by a phthalic anhydride-pyridine method (GB/T12008.3-2009), and the average molecular weight is 4039.
The structural formula of the product is as follows:
Figure GDA0004199779420000111
wherein R is 1 、R 2 、R 3 Is C 4 H 8 Or C 8 H 16 。
Comparative examples 1 to 6 and examples 1 to 6
The PC/PBT composition was prepared as follows: whether comparative example or example, according to the corresponding formulation of Table 2, PC, PBT, block copolymer and optional auxiliary agent are weighed according to the proportion, put into a high-speed mixer for mixing and stirring, the mixture is added into a weightless type feeding scale above a feeding port of a screw extruder, the temperature of a conveying section of the twin-screw extruder is controlled to be 215 ℃, the temperature of a plasticizing section is controlled to be 235 ℃, the temperature of a metering section is controlled to be 235 ℃, the rotation speed of a screw is controlled to be 400rpm, and the vacuum degree of a vacuum pumping device of the twin-screw metering section is controlled to be less than-0.7 bar. The mixture is subjected to the working procedures of blending, drawing, water cooling, air drying, granulating and drying to obtain the product.
The performance test is as follows:
weld line strength was tested according to ASTM D638 with a spline size of 63.5 x 12.7 x 3.2mm. The welding line mold is used for feeding glue from two ends of the spline to form a welding mark in the middle. The tensile rate of the weld line strength test was 50mm/min.
The ingredients of the comparative examples and examples are as follows:
20320: PC, melt flow index is 3g/10min (300 ℃, 1.2 kg), the content of terminal hydroxyl groups in the chemical production of the Wanhua is 10% of the proportion of PC terminal groups;
2074: PC, melt flow index 7g/10min (300 ℃, 1.2 kg), wanhua chemical production, hydroxyl end content accounting for 20% of PC end group proportion;
2154: PC, melt flow index is 15g/10min (300 ℃, 1.2 kg), the content of terminal hydroxyl groups in the chemical production of the Wanhua is 20% of the proportion of PC terminal groups;
2506: PC, melt flow index 50g/10min (300 ℃, 1.2 kg), wanhua chemical production, hydroxyl end content accounting for 30% of PC end group proportion;
1100-211M: PBT with a melt flow index of 20g/10min (240 ℃ C., 5 kg), produced by Taiwan vinpockels group;
1100-211A: PBT with a melt flow index of 35g/10min (240 ℃ C., 5 kg), produced by Taiwan vinpockels group;
1200-211M: PBT with a melt flow index of 70g/10min (240 ℃ C., 5 kg), produced by Taiwan vinpockels group;
1200-211D: PBT with a melt flow index of 100g/10min (240 ℃ C., 5 kg), produced by Taiwan vinpockels group;
QD-1: block copolymer-1, self-made;
QD-2: block copolymer-2, self-made;
QD-3: block copolymer-3, homemade;
QD-4: block copolymer-4, homemade;
QD-5: block copolymer-5, homemade;
AX8900: ethylene-butyl acrylate-glycidyl methacrylate copolymer, manufactured by alcoma;
1010: antioxidant, basf production;
168: antioxidant, basf production;
PETS: pentaerythritol stearate, lubricant, manufactured by Dragon Corp;
the formulations and properties of the PC/PBT compositions of comparative examples 1-6 and examples 1-6 are detailed in Table 2.
TABLE 2 formulation and Properties of the PC/PBT compositions of comparative examples 1-6 and examples 1-6
Figure GDA0004199779420000131
Figure GDA0004199779420000141
By examples 1-6 and comparative examples 1-6, the weld strength of the PC/PBT composition was significantly increased with the addition of the block copolymer, indicating that the block copolymer improved the fusion process during the melt-meeting of the PC/PBT composition, and was of great significance in the processing and shaping of the PC/PBT composition.
It will be appreciated by persons skilled in the art that the present invention is not limited to the embodiments described above, but is capable of numerous variations and modifications without departing from the spirit and scope of the invention as hereinafter claimed.

Claims (16)

1. A high weld mark strength polycarbonate/polybutylene terephthalate composition, comprising the following components:
30-70 parts by weight of polycarbonate;
25-65 parts by mass of polybutylene terephthalate;
1-5 parts by weight of a block copolymer;
wherein the block copolymer has the following structure:
Figure FDA0004047137030000011
wherein R is 1 、R 2 And R is 3 Aliphatic hydrocarbon radicals and/or alkoxy radicals having 3 to 8 carbon atoms, R 1 、R 2 And R is 3 May be the same or different; m, n and k are integers more than or equal to 1.
2. The composition of claim 1 wherein the block copolymer has a number average molecular weight of 1000 to 7000.
3. The composition according to claim 1 or 2, wherein the polycarbonate has a hydroxyl end group content of 10% to 30% of the polycarbonate end groups;
and/or the melt flow index of the polycarbonate is 3-65g/10min when tested at 300 ℃ under 1.2kg conditions.
4. The composition of claim 3, wherein the polycarbonate has a melt flow index of 7 to 50g/10min when tested at 300℃and 1.2 kg.
5. Composition according to claim 1 or 2, characterized in that the polybutylene terephthalate has a melt flow index of 20-160g/10min, measured at 240 ℃ under 5kg conditions.
6. The composition of claim 5, wherein the polybutylene terephthalate has a melt flow index of 35 to 100g/10min when tested at 240 ℃ under 5kg conditions.
7. The composition of claim 1, wherein the block copolymer is prepared by a process comprising the steps of:
s1: adding polycarbonate diol and double metal cyanide complex catalyst (DMC) into a reaction kettle to obtain a mixture a of the polycarbonate diol and DMC, introducing nitrogen to replace air, stirring, heating, and removing water in vacuum to obtain a mixture a' of the polycarbonate diol and DMC with low water content;
s2: heating the mixture a', adding part of glycidol to perform induction reaction, adding the rest of glycidol after the reaction is completed, and removing the rest of glycidol after the reaction is completed, thus obtaining the target block copolymer.
8. The composition of claim 7, wherein the polycarbonate diol of S1 is prepared by transesterification polycondensation of an aliphatic diol with one or more of dimethyl carbonate, diethyl carbonate, diphenyl carbonate;
and/or, the DMC as described in S1 is a powdery DMC catalyst taking tertiary butanol as one of the ligands;
and/or, the temperature of S1 is increased to 90-120 ℃;
and/or the mixture a' in S1 has a water content of less than 0.05% by weight.
9. The composition according to claim 8, wherein the aliphatic diol of S1 is a diol having a carbon number of not less than 3;
the number average molecular weight of the polycarbonate diol is 500-3000;
the DMC catalyst described in S1 is used in an amount of 15-500 ppm based on the sum of the mass of polycarbonate diol and the mass of all glycidol.
10. The composition of claim 9, wherein the aliphatic diol of S1 is one or more of 1, 6-hexanediol, 1, 4-butanediol, 1, 3-butanediol, trimethylpentanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, dibromoneopentyl glycol, tetrabromodipentaerythritol, 2-methyl-1, 3-propanediol, 3-methyl-1, 5-pentanediol, triethylene glycol, 1, 4-dimethylolcyclohexane, cyclohexanediol, butylethylpropanediol, diethylpentanediol, ethylhexanediol, 1, 5-pentanediol, and 1, 8-octanediol;
the number average molecular weight of the polycarbonate diol is 1000-2500;
the DMC catalyst described in S1 is used in an amount of 30-100 ppm based on the sum of the mass of polycarbonate diol and the mass of all glycidol.
11. The composition of claim 10, wherein the aliphatic diol of S1 is one or more of 1, 6-hexanediol, 1, 4-butanediol, 1, 4-dimethylolcyclohexane, diethylene glycol, 1, 8-octanediol.
12. The composition of claim 7, wherein the molar ratio of S2 to the glycidol to the polycarbonate diol is (3.5 to 75) 1;
and/or, heating the a' to 100-160 ℃ in S2;
and/or, the S2 is added with 20-80% of the total mass of the glycidol.
13. The composition of claim 12, wherein the molar ratio of S2 to the epoxypropanol to the polycarbonate diol is (7-42): 1;
and/or, the S2 is added with 20 to 60 percent of the total mass of the glycidol.
14. Composition according to claim 1, wherein optionally 0-5 parts of other adjuvants are added.
15. The composition of claim 14, wherein the auxiliary agent is selected from one or more of flame retardants, toughening agents, compatibilizers, antioxidants, lubricants, ultraviolet absorbers, light stabilizers, heat stabilizers, metal deactivators, plasticizers, antiblocking agents, colorants, coupling agents, nucleating agents, foaming agents, antibacterial agents, mold-proofing agents, acid scavengers, hydrolysis-proofing agents, chain extenders, flow modifiers, matting agents, antistatic agents, reinforcing agents, fillers, antifogging agents, light diffusers, infrared absorbers, optical brighteners, and laser marking agents.
16. A process for preparing the high weld mark strength polycarbonate/polybutylene terephthalate composition of any of claims 1-15, comprising the steps of:
SS1: premixing: the polycarbonate, the polybutylene terephthalate, the segmented copolymer and the optional auxiliary agent are weighed and mixed according to the proportion;
SS2: and (3) extruding: the mixture is extruded and granulated by a double screw extruder to obtain the polycarbonate/polybutylene terephthalate composition with high weld mark strength.
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FR1132036A (en) * 1954-05-24 1957-03-04 Bataafsche Petroleum Epoxy esters of carbonic acids and their polymers
CA1017481A (en) * 1973-01-05 1977-09-13 Charles A. Bialous Hydrolytically stable polycarbonate composition
FR2874217B1 (en) * 2004-08-10 2006-10-27 Agronomique Inst Nat Rech GLYCEROL POLYCARBONATE - ORGANIC COMPOSITIONS CONTAINING THE SAME - PROCESS FOR OBTAINING THESE ORGANIC COMPOSITIONS AND METHOD FOR EXTRACTING GLYCEROL POLYCARBONATE AND THEIR APPLICATIONS
CN103910864B (en) * 2013-01-09 2016-12-28 万华化学集团股份有限公司 A kind of preparation method of the block oligomeric diols of structure-controllable
CN104710743A (en) * 2013-12-13 2015-06-17 青岛同创节能环保工程有限公司 High-strength super-tough PC/PBT composite material and preparation method thereof
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CN104861622A (en) * 2014-11-26 2015-08-26 青岛同创节能环保工程有限公司 Flame retardation antistatic polycarbonate/polybutylene telephthalate composition
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