CN114276647A - Low-floating-fiber polyformaldehyde material as well as preparation method and application thereof - Google Patents
Low-floating-fiber polyformaldehyde material as well as preparation method and application thereof Download PDFInfo
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- CN114276647A CN114276647A CN202111382842.4A CN202111382842A CN114276647A CN 114276647 A CN114276647 A CN 114276647A CN 202111382842 A CN202111382842 A CN 202111382842A CN 114276647 A CN114276647 A CN 114276647A
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Abstract
The invention discloses a low-floating-fiber polyformaldehyde material as well as a preparation method and application thereof, and belongs to the technical field of engineering plastics. The low-floating-fiber polyformaldehyde material comprises the following components in parts by weight: 72-89 parts of polyformaldehyde, 10-25 parts of glass fiber and 0.5-2 parts of carboxyl-terminated hyperbranched polyester. According to the invention, the problem of fiber floating caused by glass fiber reinforced polyformaldehyde is effectively solved by introducing carboxyl-terminated hyperbranched polyester, the low-fiber-floating polyformaldehyde material with high strength is obtained, and the application requirements of industrial fields such as kitchenware, household appliances and automobiles requiring that the product appearance has no obvious fiber floating are met.
Description
Technical Field
The invention belongs to the technical field of engineering plastics, and particularly relates to a low-floating-fiber polyformaldehyde material as well as a preparation method and application thereof.
Background
Polyoxymethylene (POM) resins have excellent mechanical properties, abrasion resistance, high rigidity and oil resistance, and are widely used in the fields of automobiles, electronics, electrics, kitchenware, home appliances and the like. At present, the modification of POM resin mainly comprises toughening, weather resistance, wear resistance, reinforcement and the like, wherein the reinforcement is generally realized by adding glass fiber, so that the system obtains higher performance. However, the POM resin has a crystallinity of over 60 percent, a high crystallization speed and a chemical inertness of a molecular chain, so that the POM resin is not enough to wrap glass fibers, and therefore, the surface of a reinforced POM product has floating fibers and poor appearance, and the application of the POM resin is limited.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a low-floating-fiber polyformaldehyde material as well as a preparation method and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a low-floating-fiber polyformaldehyde material comprises the following components in parts by weight: 72-89 parts of polyformaldehyde, 10-25 parts of glass fiber and 0.5-2 parts of carboxyl-terminated hyperbranched polyester.
According to the invention, the carboxyl-terminated hyperbranched polyester is introduced into the system, so that on one hand, the regularity of polyformaldehyde can be destroyed, the crystallinity and regular arrangement capacity of polyformaldehyde are weakened, and the chemical inertness of polyformaldehyde molecular chains is weakened; on the other hand, the terminal carboxyl of the carboxyl-terminated hyperbranched polyester can react with the C-O bond of the polyformaldehyde and the residual hydroxyl in the glass fiber to form a bridging structure between the polyformaldehyde and the glass fiber, so that the infiltration and wrapping capacity of the polyformaldehyde on the glass fiber is improved, the infiltration of the polyformaldehyde on the glass fiber is more sufficient, and the reinforced polyformaldehyde material with low floating fiber is finally obtained.
Preferably, the low-floating-fiber polyformaldehyde material comprises the following components in parts by weight: 73.5-81 parts of polyformaldehyde, 18-25 parts of glass fiber and 0.5-1 part of carboxyl-terminated hyperbranched polyester. The low-floating-fiber polyformaldehyde material prepared according to the weight part ratio has better mechanical property.
Preferably, the carboxyl number of the carboxyl-terminated hyperbranched polyester is 6-48 mol, and the molecular weight is 1000-13200 g/mol. The hyperbranched polyesters used in the present invention may be either prepared by themselves according to the prior art or may be obtained commercially.
More preferably, the carboxyl number of the carboxyl-terminated hyperbranched polyester is 12-24 mol, and the molecular weight is 2600-6400 g/mol. The carboxyl-terminated hyperbranched polyester with the parameters has better effect of improving the floating fiber of the polyformaldehyde material.
Preferably, the melt index of the polyformaldehyde is 9-27 g/10min (190 ℃/2.16kg), and the weight-average molecular weight is 80000-160000. The melt index of the polyoxymethylene is tested according to ISO 1133-1-2011 test standard. When the polyformaldehyde with the physical and chemical parameters is adopted, the performance of the material is better. If the melt index of the polyformaldehyde is too low, the problem that the soaking and wrapping capacity of the polyformaldehyde to glass fibers is insufficient exists, so that the material performance is low, and the glass fibers are easy to expose. If the melt index of the polyformaldehyde is too high, correspondingly, the fluidity of the polyformaldehyde is also too high, so that the local glass fiber content of the material is too low, and the material performance is unstable.
Preferably, the low-floating-fiber polyformaldehyde material further comprises the following components in parts by weight: 0.1-0.5 part of main antioxidant and 0.1-0.3 part of auxiliary antioxidant, wherein the main antioxidant is hindered phenol antioxidant, and the auxiliary antioxidant is at least one of phosphite antioxidant and thioether antioxidant.
The invention also provides a preparation method of the low-floating-fiber polyformaldehyde material, which comprises the following steps:
uniformly mixing other components except the glass fiber to obtain a premix;
and adding the premix into a double-screw extruder from a main feeding port, adding the glass fibers into the double-screw extruder from a side feeding port, and performing melt extrusion, cooling and granulation through the double-screw extruder to obtain the low-floating-fiber polyformaldehyde material.
Preferably, the temperature of each barrel of the twin-screw extruder from the feeding port to the head is as follows in sequence: 150 to 170 ℃, 160 to 180 ℃, 170 to 190 ℃, 180 to 200 ℃ and 180 to 200 ℃, the screw rotation speed is 250 to 400rpm, the feeding amount is 50 to 200kg/h, and the vacuum degree is (-0.1) to 0 MPa.
The invention also provides application of the low-floating-fiber polyformaldehyde material in the industrial fields of kitchen utensils (such as knife handles), household appliances and automobiles (such as automobile lifting window gears and door handles).
The plastic part is made of the low-floating-fiber polyformaldehyde material, and is used for manufacturing kitchenware, household appliances or automobiles.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, the problem of fiber floating caused by glass fiber reinforced polyformaldehyde is effectively solved by introducing carboxyl-terminated hyperbranched polyester, the low-fiber-floating polyformaldehyde material with high strength is obtained, and the application requirements of industrial fields such as kitchenware, household appliances and automobiles requiring that the product appearance has no obvious fiber floating are met.
Detailed Description
The technical solutions of the present invention will be further described with reference to the following embodiments, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The raw materials used in the examples and comparative examples were all commercially available and were the same species for parallel experiments.
Some of the raw materials are derived from, but not limited to:
HyPer C102: carboxyl-terminated hyperbranched polyester, carboxyl number: 12mol, molecular weight: 2600g/mol, Wuhan super branched resin science and technology Limited;
HyPer C103: carboxyl-terminated hyperbranched polyester, carboxyl number: 24mol, molecular weight: 6400g/mol, Wuhan super-branched resin science and technology Limited;
HyPer C101: carboxyl-terminated hyperbranched polyester, carboxyl number: 6mol, molecular weight: 1000g/mol, Wuhan super-branched resin science and technology Limited;
HyPer C404: carboxyl-terminated hyperbranched polyester, carboxyl number: 32mol, molecular weight: 13200g/mol, Wuhan super-branched resin science and technology Limited;
HyPer C304: carboxyl-terminated hyperbranched polyester, carboxyl number: 48mol, molecular weight: 9800g/mol, Wuhan super-branched resin science and technology Limited;
HyPer H302: hydroxyl-terminated hyperbranched polyester, hydroxyl number: 10-12 mol, molecular weight: 2500g/mol, Wuhan super branched resin science and technology Limited;
CYD-5300: end-capped hyperbranched polyester, no end groups, a molecular weight of 900g/mol, Waishaheng molecular New materials, Inc.;
polyoxymethylene POM M25: the melt index is 2.5g/10min (190 ℃/2.16kg), the weight average molecular weight is 220000, and the Yunnan chemical Co., Ltd;
polyoxymethylene POM M90: the melt index is 9g/10min (190 ℃/2.16kg), the weight average molecular weight is 160000, Yunnan chemical Co., Ltd;
polyoxymethylene POM M270: the melt index is 27g/10min (190 ℃/2.16kg), the weight average molecular weight is 80000, Yunnan chemical Co., Ltd;
polyoxymethylene POM M450: the melting index is 45g/10min (190 ℃/2.16kg), the weight average molecular weight is 60000, Yunnan chemical Co., Ltd;
ECS 10-3.0-T445: alkali-free chopped glass fiber, taishan glass fiber ltd;
primary antioxidants, hindered phenol antioxidants, bis [3- (1, 1-dimethylethyl) -4-hydroxy-5-methylpropanoic acid ] tripeleneglycol, commercially available;
secondary antioxidant, phosphite antioxidant, tris (2, 4-di-tert-butylphenyl) phosphite, commercially available.
The test method is as follows:
(1) floating fiber evaluation method
Using a bandaid injection molding machine (model BS80-III), plaques were injection molded, and the plaque surface was observed to assess the degree of fiber floating. The injection molding process comprises the following steps: the material temperature is 200 ℃, the injection speed is medium-high speed, and the mold temperature is 80 ℃.
Visually inspecting and grading floating fibers:
level 1: no floating fiber exists, no floating fiber exists on the surface of the color plate, and the appearance is excellent;
and 2, stage: the floating fibers are less, and the surface of the color plate only has slight floating fibers, so the appearance is better;
and 3, level: the floating fibers are more, the surface of the color plate has more floating fibers, and the appearance is poorer;
4, level: the floating fiber is serious, the floating fiber on the surface of the color plate is very serious, and the appearance is poor.
(2) Tensile strength: test standard ISO 527-2-2012, test speed 10 mm/min.
Examples 1 to 13
Embodiments 1 to 13 provide a low-floating-fiber polyformaldehyde material, the weight part formula of which is shown in tables 1 to 2, and the preparation method comprises the following steps:
(1) adding polyformaldehyde, carboxyl-terminated hyperbranched polyester, a main antioxidant and an auxiliary antioxidant into a high-speed mixer together, and mixing for 2-5 min to uniformly mix the raw materials to obtain a premix;
(2) adding the premix into a double-screw extruder from a main feeding port, adding the glass fibers into the double-screw extruder from a side feeding port, and performing melt extrusion, cooling and granulation through the double-screw extruder to obtain the low-floating-fiber polyformaldehyde material. Wherein, the temperature of each screw cylinder of double screw extruder from the charge door to the aircraft nose is in proper order: 150 to 170 ℃, 160 to 180 ℃, 170 to 190 ℃, 180 to 200 ℃ and 180 to 200 ℃, the screw rotation speed is 250 to 400rpm, the feeding amount is 50 to 200kg/h, and the vacuum degree is (-0.1) to 0 MPa.
Comparative examples 1 to 6
Comparative examples 1 to 6 provide polyoxymethylene materials having the weight parts as shown in Table 2, and the preparation methods refer to those of examples 1 to 13.
TABLE 1
Note: in the table, "-" indicates that the component was not added, as follows.
TABLE 2
As can be seen from the test results of tables 1-2 above: the polyformaldehyde material prepared by the embodiment of the invention has the characteristic of low fiber floating, and the tensile strength reaches 86.4-128.2 MPa (the tensile strength is more than or equal to 80MPa, so that the product requirement can be met).
In the formula system, the addition ratio of the components can affect the tensile strength and fiber floating condition of the material. In comparative example 5, the tensile strength of the material is significantly reduced to only 65.2MPa due to the addition of too little glass fiber. In comparative example 6, the amount of floating fibers on the surface of the material was high due to the addition of too much glass fibers, and reached level 3. Secondly, in comparative example 1, the fiber floating on the surface of the material is severe and reaches level 4 because the carboxyl-terminated hyperbranched polyester is not added. In comparative example 2, the tensile strength of the material is reduced to 106.3MPa due to the excessive addition of the carboxyl-terminated hyperbranched polyester, and the surface fiber floating is large and reaches 3 grades. When the composite material is added according to the formula disclosed by the invention, the material not only has higher tensile strength, but also has less surface floating fiber and better comprehensive performance. According to the formula, 73.5-81 parts by weight of polyformaldehyde, 18-25 parts by weight of glass fiber and 0.5-1 part by weight of carboxyl-terminated hyperbranched polyester are adopted, so that the tensile strength of the material is higher and reaches 111.1-128.2 MPa, and the surface has less fiber floating and reaches level 1.
Comparing examples 2 and 7-10, it can be seen that the number of carboxyl groups and the molecular weight of the carboxyl-terminated hyperbranched polyester can affect the performance of the material, and when the number of carboxyl groups and the molecular weight of the carboxyl-terminated hyperbranched polyester are 12-24 mol and 2600-6400 g/mol, the material not only has high strength, but also has less surface floating fibers.
It can be seen from comparative examples 3 and 4 that the problem of fiber floating on the surface of the POM material cannot be effectively improved when the hydroxyl-terminated hyperbranched polyester or the end-capped hyperbranched polyester is used to replace the carboxyl-terminated hyperbranched polyester.
It can be seen from the comparison between example 2 and examples 11-13 that the melt index (i.e., melt index) and the weight average molecular weight of POM also affect the performance of the material, and the material has better performance when the melt index of the polyoxymethylene used is 9-27 g/10min (190 ℃/2.16kg) and the weight average molecular weight is 80000-160000.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The low-floating-fiber polyformaldehyde material is characterized by comprising the following components in parts by weight: 72-89 parts of polyformaldehyde, 10-25 parts of glass fiber and 0.5-2 parts of carboxyl-terminated hyperbranched polyester.
2. The low-floating-fiber polyoxymethylene material according to claim 1, comprising the following components in parts by weight: 73.5-81 parts of polyformaldehyde, 18-25 parts of glass fiber and 0.5-1 part of carboxyl-terminated hyperbranched polyester.
3. The low-floating-fiber polyformaldehyde material as claimed in claim 1 or 2, wherein the carboxyl-terminated hyperbranched polyester has a carboxyl number of 6-48 mol and a molecular weight of 1000-13200 g/mol.
4. The low-floating-fiber polyformaldehyde material as claimed in claim 3, wherein the carboxyl-terminated hyperbranched polyester has a carboxyl number of 12-24 mol and a molecular weight of 2600-6400 g/mol.
5. The low-blooming polyoxymethylene material of claim 1 or 2, wherein the polyoxymethylene has a melt index of 9 to 27g/10min (190 ℃/2.16kg) and a weight average molecular weight of 80000 to 160000.
6. The low-floating-fiber polyoxymethylene material according to claim 1 or 2, further comprising the following components in parts by weight: 0.1-0.5 part of main antioxidant and 0.1-0.3 part of auxiliary antioxidant, wherein the main antioxidant is hindered phenol antioxidant, and the auxiliary antioxidant is at least one of phosphite antioxidant and thioether antioxidant.
7. The method for preparing the low-floating-fiber polyformaldehyde material as claimed in any one of claims 1-6, wherein the method comprises the following steps:
uniformly mixing other components except the glass fiber to obtain a premix;
and adding the premix into a double-screw extruder from a main feeding port, adding the glass fibers into the double-screw extruder from a side feeding port, and performing melt extrusion, cooling and granulation through the double-screw extruder to obtain the low-floating-fiber polyformaldehyde material.
8. The method for preparing the low-floating-fiber polyformaldehyde material as claimed in claim 7, wherein the temperatures of all cylinders of the twin-screw extruder from the feed inlet to the nose are as follows in sequence: 150 to 170 ℃, 160 to 180 ℃, 170 to 190 ℃, 180 to 200 ℃ and 180 to 200 ℃, the screw rotation speed is 250 to 400rpm, the feeding amount is 50 to 200kg/h, and the vacuum degree is (-0.1) to 0 MPa.
9. Use of a low-profile polyoxymethylene material according to any of claims 1 to 6 in the fields of kitchen appliances, household appliances and automotive industry.
10. A plastic part, which is characterized by being made of the low-floating-fiber polyformaldehyde material as defined in any one of claims 1-6, and the plastic part is used for manufacturing kitchen utensils, household appliances or automobiles.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101044191A (en) * | 2004-10-20 | 2007-09-26 | 巴斯福股份公司 | Free-flowing polyoxymethylenes |
| CN102329471A (en) * | 2011-06-24 | 2012-01-25 | 深圳市科聚新材料有限公司 | Fiberglass-reinforced polyformaldehyde material and preparation method thereof |
| CN107286676A (en) * | 2017-07-28 | 2017-10-24 | 张乃斌 | A kind of synergist for adding dissaving polymer |
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- 2021-11-19 CN CN202111382842.4A patent/CN114276647B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101044191A (en) * | 2004-10-20 | 2007-09-26 | 巴斯福股份公司 | Free-flowing polyoxymethylenes |
| CN102329471A (en) * | 2011-06-24 | 2012-01-25 | 深圳市科聚新材料有限公司 | Fiberglass-reinforced polyformaldehyde material and preparation method thereof |
| CN107286676A (en) * | 2017-07-28 | 2017-10-24 | 张乃斌 | A kind of synergist for adding dissaving polymer |
Non-Patent Citations (2)
| Title |
|---|
| 李建华;金旺;王亚涛;王军;陆亦军;: "长玻纤增强聚甲醛注塑成型工艺的研究" * |
| 梁叶云等: "超支化聚酯制备高玻纤含量的尼龙/玻纤复合材料" * |
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