CN111073233A - High-toughness PBT (polybutylene terephthalate) composite material as well as preparation method and application thereof - Google Patents
High-toughness PBT (polybutylene terephthalate) composite material as well as preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920001707 polybutylene terephthalate Polymers 0.000 title claims description 62
- -1 polybutylene terephthalate Polymers 0.000 title description 4
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 43
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000012745 toughening agent Substances 0.000 claims abstract description 6
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 32
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 18
- 229920006225 ethylene-methyl acrylate Polymers 0.000 claims description 9
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229920005906 polyester polyol Polymers 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 125000005442 diisocyanate group Chemical group 0.000 claims description 4
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 3
- 150000002009 diols Chemical class 0.000 claims description 3
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical group O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- VOXZDWNPVJITMN-ZBRFXRBCSA-N 17β-estradiol Chemical compound OC1=CC=C2[C@H]3CC[C@](C)([C@H](CC4)O)[C@@H]4[C@@H]3CCC2=C1 VOXZDWNPVJITMN-ZBRFXRBCSA-N 0.000 claims description 2
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 2
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 229920001897 terpolymer Polymers 0.000 claims description 2
- 229920001971 elastomer Polymers 0.000 abstract description 9
- 239000000806 elastomer Substances 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 229920001296 polysiloxane Polymers 0.000 description 8
- 238000005303 weighing Methods 0.000 description 6
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 description 1
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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
- 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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- 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
- C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers
Abstract
The invention discloses a high-toughness PBT composite material, a preparation method and an application thereof, wherein the material is prepared from the following raw materials in parts by weight: 40-70% of PBT; 10-35% of TPU; 2-15% of a compatilizer; 2-10% of a toughening agent; 0.1-5% of an auxiliary agent. The preparation method of the composite material is realized by adopting a high-speed kneader and a double-screw extruder, and is simple to prepare and easy to implement. The TPU material is synthesized by a two-step method, and a polyurethane prepolymer with certain viscosity is obtained in the first step. And secondly, heating to 40-85 ℃, dropwise adding BDO into the polyurethane prepolymer, and continuously reacting for 2-5 h after dropwise adding is finished, so as to generate the TPU elastomer with high molecular weight. In the invention, the TPU has good toughness and high strength, and has good compatibility with PBT, thereby ensuring the excellent impact property of the composite material.
Description
Technical Field
The invention relates to the technical field of PBT composite materials, in particular to a high-toughness PBT composite material and a preparation method and application thereof.
Background
Polybutylene terephthalate (PBT) as one of five engineering plastics has good heat resistance, electrical insulation, chemical resistance, lubricity and excellent mechanical properties, and is widely applied to the fields of automobile parts and electronic and electrical appliances. As the consumption of PBT increases, higher requirements are put on the performance of the PBT, so the research on the performance and the application of the PBT is mainly focused on the aspect of physical modification at present. The pure PBT has small notched impact strength and non-notched impact strength of the suspended beam, and is easy to deform and break under a certain load condition, so that the use of the PBT is greatly limited, and the PBT must be toughened and modified. To solve the problem, the invention synthesizes TPU through a two-step method, and is used for improving the toughness of PBT.
The Chinese invention patent application with the application publication number of CN 109370199A (with the application number of 201811271981.8) discloses a high-toughness and high-elongation modified copolymer, which comprises the following main components in percentage by mass: 20-40% of PBT, 20-40% of TPU and 20-40% of TPEE; the health-care food also comprises the following auxiliary components: 0.8-1.5% of lubricant based on the mass ratio of the main component. The technical scheme is that the PBT is a common optical cable loose sleeve material, the toughness and the elongation of the TPU are both excellent and are close to rubber, and the toughness of the PBT is greatly improved.
Disclosure of Invention
The invention provides a high-toughness PBT composite material, and a preparation method and application thereof.
A high-toughness PBT composite material is prepared from the following raw materials in percentage by weight:
further preferably, the high-toughness PBT composite material is prepared from the following raw materials in percentage by weight:
the PBT can adopt a commercially available general model.
The ASA (acrylic Styrene acrylate copolymer) is engineering plastic and is a graft copolymer of acrylate rubber bodies, acrylonitrile and Styrene
The compatilizer is maleic anhydride grafted acrylonitrile-butadiene-styrene terpolymer (ABS-g-MAH);
the toughening agent is one or two of ethylene-methyl acrylate copolymer (EMA) and methyl methacrylate-butadiene-styrene terpolymer (MBS).
The auxiliary agent is one or more than two (including two) of ultraviolet absorbent, lubricant, antioxidant and the like.
The TPU has good toughness and excellent performance, and has good compatibility with the PBT, so that the excellent impact property of the composite material is ensured.
More preferably, the high-toughness PBT composite material is prepared from the following raw materials in percentage by weight:
the compatilizer is maleic anhydride grafted acrylonitrile-butadiene-styrene terpolymer (ABS-g-MAH);
the toughening agent is ethylene-methyl acrylate copolymer (EMA).
The invention also provides a preparation method of the TPU, which adopts a two-step method and a process route, and has the advantages of simple preparation, easy implementation and strong operability.
A process for preparing a TPU comprising the steps of:
1) butanone is added into the macrodiol and the diisocyanate, and dibutyltin dilaurate (DBTDL) serving as a catalyst is added into the mixture to react for 2 to 5 hours at the temperature of 65 to 120 ℃ to obtain the polyurethane prepolymer.
2) Heating the polyurethane prepolymer obtained in the step 1) to 40-85 ℃, dropwise adding a butanone solution of 1, 4-butanediol into the polyurethane prepolymer, and continuously reacting for 2-5 h after dropwise adding is finished to obtain the TPU.
The macromolecular dihydric alcohol is one of polyester polyol, polycaprolactone polyol and polycarbonate diol.
The diisocyanate is one of Lysine Diisocyanate (LDI), Toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), Hexamethylene Diisocyanate (HDI), diphenylmethane diisocyanate (MDI) and dicyclohexylmethane diisocyanate (HMDI).
Most preferably, the preparation method comprises the following steps:
1) adding polyester polyol and isophorone diisocyanate into a three-neck flask, adding butanone, starting stirring, adding a catalyst dibutyltin dilaurate (DBTDL), adding a condensing tube for refluxing, and reacting at the temperature of 80-90 ℃ for 2-4 hours to obtain a polyurethane prepolymer;
2) heating the polyurethane prepolymer obtained in the step 1) to 60-70 ℃, dissolving 1, 4-Butanediol (BDO) in butanone to prepare a butanone solution with the mass percent of 1, 4-butanediol being 25% -35%, dropwise adding the butanone solution into the polyurethane prepolymer, and continuously reacting for 3-5 hours after dropwise adding is finished to obtain the TPU.
A preparation method of a high-toughness PBT composite material comprises the following steps:
1) preparing TPU;
2) and uniformly mixing the PBT, the TPU, the toughening agent, the compatilizer, the auxiliary agent and the ASA which can be selectively added, adding the mixture into a double-screw extruder, and granulating the mixture by a tractor to obtain the high-toughness PBT composite material.
In the step 2), the conditions for uniform mixing are as follows: the components are placed in a high-speed kneader, the rotating speed is kept at 500-.
The temperature of each area from the feed inlet to the machine head of the double-screw extruder is as follows: the temperature of the first zone is 195-215 ℃, the temperature of the second zone is 210-230 ℃, the temperature of the third zone is 230-240 ℃, the temperature of the fourth zone is 240-250 ℃, the temperature of the fifth zone is 245-250 ℃, the temperature of the sixth zone is 235-250 ℃, the temperature of the seventh zone is 240-250 ℃, the temperature of the head is 240-250 ℃, and the rotating speed is 50-350 rpm/min.
The high-toughness PBT composite material has excellent impact property and good low-temperature toughness, and is suitable for being used as parts in severe cold regions, outdoor pipeline accessories and bumpers.
Compared with the prior art, the invention has the following advantages
The TPU has good toughness and excellent performance, and has good compatibility with the PBT, so that the excellent impact property of the composite material is ensured. The PBT/TPU alloy disclosed by the invention is good in low-temperature toughness and suitable for being used as parts in severe cold regions, outdoor pipeline fittings and bumpers.
The preparation method of the high-toughness PBT composite material is simple in preparation, easy to implement, strong in operability, beneficial to industrial large-scale production and wide in application prospect.
Drawings
FIG. 1 is a chart of the infrared spectrum of the TPU elastomer prepared in preparation example 1 of this invention with the abscissa being the wavenumber and the ordinate being the intensity.
Detailed Description
The present invention will be described in detail below by way of examples, which are provided to better illustrate the present invention, but are not limited to the examples.
Preparation example 1
A process for preparing a TPU comprising the steps of:
1)11g of polyester polyol (XCP-355, Asahi Sichuan chemical Co., Ltd.) and 21g of isophorone diisocyanate (IPDI) are added into a three-neck flask, 50g of butanone is added, stirring is started, 0.1g of catalyst dibutyltin dilaurate (DBTDL) is added, a condensing tube is added for refluxing, and after reaction is carried out for 3 hours at the temperature of 85 ℃, a polyurethane prepolymer with certain viscosity can be obtained.
2) Heating the polyurethane prepolymer with certain viscosity obtained in the step 1) to 65 ℃, weighing 5g of 1, 4-Butanediol (BDO), dissolving the 1, 4-Butanediol (BDO) in butanone to prepare a butanone solution with the mass percent of 1, 4-butanediol of 30%, dropwise adding the butanone solution into the polyurethane prepolymer from a dropping funnel, and continuously reacting for 4 hours after dropwise adding is finished, so as to generate a high-molecular-weight TPU elastomer, namely TPU.
The prepared TPU elastomer can be seen by an infrared spectrum (figure 1) of 1734cm-1The left and right have-CO-characteristic absorption peak in-COO-NH-group, 1535cm-1There is an absorption peak of-NH-, so that the sample contains-COO-NH-groups. The product prepared in this example was a polyurethane.
The molecular weight of the prepared TPU elastomer is measured by adopting gel permeation chromatography, the relative molecular mass and the distribution of a sample are measured by adopting a PL-GPC220 gel permeation chromatograph, chloroform is used as a solvent, the sample introduction amount is 1.0mL/min, and the test temperature is 80 ℃.
The parameters of the prepared TPU elastomer are shown in Table 1.
TABLE 1 composition molar ratio, molecular weight and mechanical Properties of the polyurethanes
The parameters of a commercial WHT-1195 Tantawawa TPU are shown in Table 2.
TABLE 2
Example 1
The components were weighed according to table 3 below:
TABLE 3
1. Weighing the dried PBT, EMA, TPU, ABS-g-MAH, anti-UV-P, EBS, silicone, 1010 and 168 according to the weight percentage formula;
2. placing the weighed components in a high-speed mixer at the rotating speed of 2500rpm/min for 20 min;
4. adding the uniformly mixed PBT, EMA, TPU, ABS-g-MAH, UV-resistant P, EBS, silicone, 1010 and 168 into a feeding funnel of a double-screw extruder, wherein the parameters of the double-screw extruder are as follows: the temperature of the first zone is 195 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 230 ℃, the temperature of the fourth zone is 240 ℃, the temperature of the fifth zone is 245 ℃, the temperature of the sixth zone is 245 ℃, the temperature of the seventh zone is 250 ℃, the temperature of a machine head is 250 ℃, the rotating speed is 300rpm/min, and the high-toughness PBT composite material is obtained after being pulled and granulated by a tractor.
Example 2
The components were weighed according to table 4 below:
TABLE 4
1. Weighing the dried PBT, EBA, TPU, ABS-g-MAH, anti-UV-770, TAF, silicone, 1098 and 168 according to the weight percentage formula;
2. placing the weighed components in a high-speed mixer at the rotating speed of 2500rpm/min for stirring for 30 min;
3. adding the uniformly mixed PBT, EBA, TPU, ABS-g-MAH, anti-UV-770, TAF, silicone, 1098 and 168 into a feeding funnel of a double-screw extruder, wherein the parameters of the double-screw extruder are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 230 ℃, the temperature of the fourth zone is 250 ℃, the temperature of the fifth zone is 250 ℃, the temperature of the sixth zone is 250 ℃, the temperature of the seventh zone is 250 ℃, the temperature of the machine head is 250 ℃, the rotating speed is 350rpm/min, and the high-toughness PBT composite material is obtained after being pulled and granulated by a tractor.
Example 3
The components were weighed according to table 5 below:
TABLE 5
1. Weighing the dried PBT, EBA, TPU, ABS-g-MAH, anti-UV-327, TAF, silicone, 1076 and 168 according to the weight percentage formula;
2. placing the weighed components in a high-speed mixer at the rotating speed of 3500pm/min for 20 min;
3. adding the uniformly mixed PBT, EBA, TPU, ABS-g-MAH, anti-UV-327, TAF, silicone, 1076 and 168 into a feeding funnel of a double-screw extruder, wherein the parameters of the double-screw extruder are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 230 ℃, the temperature of the fourth zone is 245 ℃, the temperature of the fifth zone is 250 ℃, the temperature of the sixth zone is 250 ℃, the temperature of the seventh zone is 250 ℃, the temperature of a machine head is 250 ℃, the rotating speed is 350rpm/min, and after the PBT/ASA alloy particles are drawn and granulated by a traction machine, the PBT/ASA alloy particles, namely the high-toughness PBT composite material, are obtained.
Example 4
The components were weighed according to table 6 below:
TABLE 6
1. Weighing the dried PBT, EBA, TPU, ABS-g-MAH, anti-UV-P, TAF, white oil, 1010 and 168 according to the weight percentage formula;
2. placing the weighed components in a high-speed mixer at the rotating speed of 3000pm/min for stirring for 30 min;
3. adding the uniformly mixed PBT, EBA, TPU, ABS-g-MAH, anti-UV-P, TAF, white oil, 1010, 168 and ZnO powder into a feeding funnel of a double-screw extruder, wherein the parameters of the double-screw extruder are as follows: the temperature of the first zone is 200 ℃, the temperature of the second zone is 225 ℃, the temperature of the third zone is 235 ℃, the temperature of the fourth zone is 245 ℃, the temperature of the fifth zone is 245 ℃, the temperature of the sixth zone is 250 ℃, the temperature of the seventh zone is 250 ℃, the temperature of a machine head is 250 ℃, the rotating speed is 350rpm/min, and the high-toughness PBT composite material is obtained after being pulled and granulated by a tractor.
Example 5
The components were weighed according to table 7 below:
TABLE 7
1. Weighing the dried PBT, EMA, ASA, TPU, ABS-g-MAH, anti-UV-P, EBS, silicone, 1010 and 168 according to the weight percentage formula;
2. placing the weighed components in a high-speed mixer at the rotating speed of 2500rpm/min for 20 min;
4. adding the uniformly mixed PBT, EMA, TPU, ABS-g-MAH, UV-resistant P, EBS, silicone, 1010 and 168 into a feeding funnel of a double-screw extruder, wherein the parameters of the double-screw extruder are as follows: the temperature of the first zone is 195 ℃, the temperature of the second zone is 210 ℃, the temperature of the third zone is 230 ℃, the temperature of the fourth zone is 240 ℃, the temperature of the fifth zone is 245 ℃, the temperature of the sixth zone is 245 ℃, the temperature of the seventh zone is 250 ℃, the temperature of a machine head is 250 ℃, the rotating speed is 300rpm/min, and the high-toughness PBT composite material is obtained after being pulled and granulated by a tractor.
The test results of the high-toughness PBT composite material prepared in the embodiments 1-5 of the invention are shown in Table 8.
TABLE 8
From the data in Table 8, the PBT has good low-temperature toughness, and is suitable for being used as parts in severe cold regions, outdoor pipeline accessories and bumpers. Examples 1 to 3 adopt the TPU elastomer prepared by the invention, and example 4 adopts a commercially available TPU, compared with example 4, examples 1 to 3 show more excellent mechanical properties and performances, and examples 1 to 3 have more excellent impact properties and good low-temperature toughness. Therefore, the self-made TPU disclosed by the invention can enable the composite material to have more excellent mechanical properties and better low-temperature properties, and is suitable for serving as parts in severe cold regions, outdoor pipeline fittings and bumpers. Compared with the example 1, the ASA is added, and the components in the example 5 interact and cooperate with each other, so that the high-impact-resistance high-toughness high-impact-resistance high-toughness-resistance high-impact-resistance.
Claims (10)
1. The high-toughness PBT composite material is characterized by being prepared from the following raw materials in percentage by weight:
2. the high-toughness PBT composite material according to claim 1, wherein the composite material is prepared from the following raw materials in percentage by weight:
3. a high toughness PBT composite material according to claim 1 or 2, wherein the compatibilizer is maleic anhydride grafted acrylonitrile-butadiene-styrene terpolymer;
the toughening agent is one or two of ethylene-methyl acrylate copolymer and methyl methacrylate-butadiene-styrene terpolymer.
4. A preparation method of the high-toughness PBT composite material according to any one of claims 1 to 3, characterized by comprising the following steps:
1) preparing TPU;
2) uniformly mixing PBT, TPU, a toughening agent, a compatilizer, an auxiliary agent and optionally added ASA, adding the mixture into a double-screw extruder, and granulating the mixture by a tractor to obtain the high-toughness PBT composite material.
5. The preparation method of the high-toughness PBT composite material according to claim 4, wherein the step 1) of preparing the TPU specifically comprises:
1) butanone is added into the macromolecular diol and the diisocyanate, and then the catalyst dibutyltin dilaurate is added, so that the polyurethane prepolymer is obtained after the reaction is carried out for 2-5 h at the temperature of 65-120 ℃.
2) Heating the polyurethane prepolymer obtained in the step 1) to 40-85 ℃, dropwise adding a butanone solution of 1, 4-butanediol into the polyurethane prepolymer, and continuously reacting for 2-5 h after dropwise adding is finished to obtain the TPU.
6. The preparation method of the high-toughness PBT composite material according to claim 5, wherein the macrodiol is one of polyester polyol, polycaprolactone polyol and polycarbonate diol;
the diisocyanate is one of lysine diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate and dicyclohexylmethane diisocyanate.
7. The preparation method of the high-toughness PBT composite material according to claim 4, wherein the step 1) of preparing the TPU specifically comprises:
1) adding polyester polyol and isophorone diisocyanate into a three-neck flask, adding butanone, starting stirring, adding a catalyst dibutyltin dilaurate, adding a condensing tube for refluxing, and reacting at the temperature of 80-90 ℃ for 2-4 hours to obtain a polyurethane prepolymer;
2) heating the polyurethane prepolymer obtained in the step 1) to 60-70 ℃, dissolving 1, 4-Butanediol (BDO) in butanone to prepare a butanone solution with the mass percent of 1, 4-butanediol being 25% -35%, dropwise adding the butanone solution into the polyurethane prepolymer, and continuously reacting for 3-5 hours after dropwise adding is finished to obtain the TPU.
8. The preparation method of the high-toughness PBT composite material according to claim 4, wherein in the step 2), the mixing conditions are as follows: the components are placed in a high-speed kneader, the rotating speed is kept at 500-.
9. The preparation method of the high-toughness PBT composite material according to claim 4, wherein in the step 2), the temperature of each zone from the feeding port to the head of the twin-screw extruder is as follows: the temperature of the first zone is 195-215 ℃, the temperature of the second zone is 210-230 ℃, the temperature of the third zone is 230-240 ℃, the temperature of the fourth zone is 240-250 ℃, the temperature of the fifth zone is 245-250 ℃, the temperature of the sixth zone is 235-250 ℃, the temperature of the seventh zone is 240-250 ℃, the temperature of the head is 240-250 ℃, and the rotating speed is 50-350 rpm/min.
10. Use of the high tenacity PBT composite according to claim 1 or 2 in the manufacture of outdoor pipe fittings and bumpers.
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