CN114276647B - Low-floating-fiber polyformaldehyde material and preparation method and application thereof - Google Patents
Low-floating-fiber polyformaldehyde material and preparation method and application thereof Download PDFInfo
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- CN114276647B CN114276647B CN202111382842.4A CN202111382842A CN114276647B CN 114276647 B CN114276647 B CN 114276647B CN 202111382842 A CN202111382842 A CN 202111382842A CN 114276647 B CN114276647 B CN 114276647B
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Abstract
The invention discloses a low-floating-fiber polyformaldehyde material, 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, through introducing carboxyl-terminated hyperbranched polyester, the fiber floating problem caused by glass fiber reinforced polyformaldehyde is effectively improved, the low-fiber polyformaldehyde material with high strength is obtained, and the application requirements of industrial fields such as kitchen appliances, household appliances, automobiles and the like requiring products without obvious fiber floating in appearance are met.
Description
Technical Field
The invention belongs to the technical field of engineering plastics, and particularly relates to a low-fiber-floating polyoxymethylene material, a preparation method and application thereof.
Background
Polyoxymethylene (POM) resin has excellent mechanical properties, wear resistance, high rigidity and oil resistance, and is widely used in the fields of automobiles, electronics and electricity, kitchen appliances, 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, since the crystallinity of the POM resin is up to more than 60%, the crystallization speed is high, and the molecular chain is chemically inert, the glass fiber is not fully wrapped, so that the surface of the reinforced POM product is provided with floating fiber, the appearance is poor, and the application of the reinforced POM product is limited.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a low-fiber-floating polyformaldehyde material and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the low-floating fiber polyoxymethylene 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, carboxyl-terminated hyperbranched polyester is introduced into the system, so that on one hand, the regularity of the polyformaldehyde can be destroyed, the crystallinity and the regular arrangement capacity of the polyformaldehyde are weakened, and the chemical inertness of a polyformaldehyde molecular chain is weakened; on the other hand, the carboxyl end groups of the carboxyl end hyperbranched polyester can act with C-O bonds of the polyformaldehyde and residual hydroxyl in the glass fiber to form a bridging structure between the polyformaldehyde and the glass fiber, so that the infiltration wrapping capability of the polyformaldehyde on the glass fiber is improved, the infiltration of the polyformaldehyde on the glass fiber is more sufficient, and finally the reinforced polyformaldehyde material with low floating fiber is obtained.
Preferably, the low-floating-fiber polyoxymethylene material comprises the following components in parts by weight: 73.5 to 81 parts of polyformaldehyde, 18 to 25 parts of glass fiber and 0.5 to 1 part of carboxyl-terminated hyperbranched polyester. The low-fiber-floating polyoxymethylene material prepared according to the weight part has better mechanical properties.
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 polyester used in the invention can be self-made according to the prior art, and can also be obtained through commercial purchase.
More preferably, the carboxyl group number of the carboxyl group-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 polyoxymethylene material.
Preferably, the melt index of the polyoxymethylene is 9 to 27g/10min (190 ℃ C./2.16 kg), and the weight average molecular weight is 80000 to 160000. The melt index of the polyoxymethylene was tested according to ISO 1133-1-2011 test standard. When the polyoxymethylene with the physicochemical parameters is adopted, the material performance is better. If the melt index of the polyformaldehyde is too low, the problem of insufficient infiltration and wrapping capacity of the polyformaldehyde on the glass fiber exists, so that the material performance is low, and the glass fiber is exposed easily. If the melt index of the polyformaldehyde is too high, the fluidity of the polyformaldehyde is too high correspondingly, so that the local glass fiber content of the material is too low, and the material performance is unstable.
Preferably, the low-floating-fiber polyoxymethylene 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 polyoxymethylene material, which comprises the following steps:
uniformly mixing other components except glass fibers to obtain a premix;
and adding the premix into a double-screw extruder from a main feeding port, adding 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 screw barrel from the feed inlet to the machine head of the double-screw extruder is as follows: 150-170 ℃, 160-180 ℃, 170-190 ℃, 180-200 ℃ and 180-200 ℃, the screw speed is 250-400 rpm, the feeding amount is 50-200 kg/h, and the vacuum degree is (-0.1) to 0MPa.
The invention also provides application of the low-floating-fiber polyoxymethylene 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).
A plastic part made of the low-fiber polyoxymethylene material, which is used for manufacturing kitchen appliances, home appliances or automobiles.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, through introducing carboxyl-terminated hyperbranched polyester, the fiber floating problem caused by glass fiber reinforced polyformaldehyde is effectively improved, the low-fiber polyformaldehyde material with high strength is obtained, and the application requirements of industrial fields such as kitchen appliances, household appliances, automobiles and the like requiring products without obvious fiber floating in appearance are met.
Detailed Description
The technical solution of the present invention will be further described with reference to the embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The starting materials used in the examples and comparative examples were all commercially available and were the same for the parallel experiments.
Some sources of raw materials are as follows, but are not limited to these:
HyPer C102: carboxyl-terminated hyperbranched polyester, carboxyl number: 12mol, molecular weight: 2600g/mol, WU hyperbranched resin technology Co., ltd;
HyPer C103: carboxyl-terminated hyperbranched polyester, carboxyl number: 24mol, molecular weight: 6400g/mol, WU hyperbranched resin technology Co., ltd;
HyPer C101: carboxyl-terminated hyperbranched polyester, carboxyl number: 6mol, molecular weight: 1000g/mol, WUHANZHUYUN resin technologies Co., ltd;
HyPer C404: carboxyl-terminated hyperbranched polyester, carboxyl number: 32mol, molecular weight: 13200g/mol, WU hyperbranched resin science and technology Co., ltd;
HyPer C304: carboxyl-terminated hyperbranched polyester, carboxyl number: 48mol, molecular weight: 9800g/mol, WUHANZHUBranch resin technologies Co., ltd;
HyPer H302: hydroxyl-terminated hyperbranched polyesters, hydroxyl number: 10-12 mol, molecular weight: 2500g/mol, WUHANZHUZU resin technology Co., ltd;
CYD-5300: blocked hyperbranched polyesters, endless, molecular weight 900g/mol, wihai morning source molecular New Material Co., ltd;
polyoxymethylene POM M25: melt index 2.5g/10min (190 ℃ C./2.16 kg), weight average molecular weight 220000, yunnan Yuntian Co., ltd;
polyoxymethylene POM M90: 9g/10min (190 ℃/2.16 kg) of melt finger, 160000 weight average molecular weight, yunnan Yuntian Co., ltd;
polyoxymethylene POM M270: melt finger 27g/10min (190 ℃ C./2.16 kg), weight average molecular weight 80000, yunnan Yuntian Co., ltd;
polyoxymethylene POM M450: 45g/10min (190 ℃/2.16 kg) of melt finger, 60000 of weight average molecular weight, yunnan Yuntian Co., ltd;
ECS10-3.0-T445: alkali-free chopped glass fibers, taishan glass fiber Inc.;
primary antioxidants, hindered phenolic antioxidants, bis [3- (1, 1-dimethylethyl) -4-hydroxy-5-methylbenzoic acid ] tri-polyethylene glycol, commercially available;
auxiliary antioxidants, phosphite antioxidants, tris (2, 4-di-t-butylphenyl) phosphite, commercially available.
The test method is as follows:
(1) Floating fiber evaluation method
The panel was injection molded using a Bowound injection molding machine (model BS 80-III), the surface of the panel was observed, and the degree of float was evaluated. An injection molding process comprises the following steps: the material temperature is 200 ℃, the injection speed is high, and the die temperature is 80 ℃.
Visual inspection of float fiber grading:
stage 1: the surface of the color plate has no floating fiber, and the appearance is excellent;
2 stages: the floating fibers are less, the surface of the color plate is only slightly floating fibers, and the appearance is good;
3 stages: the surface of the color plate has more floating fibers and the appearance is poor;
4 stages: the floating fiber is serious, the floating fiber on the surface of the color plate is serious, and the appearance is poor.
(2) Tensile strength: test standard ISO 527-2-2012, test speed 10mm/min.
Examples 1 to 13
Examples 1-13 provide a low-fiber polyoxymethylene material, the formula of which in parts by weight is shown in tables 1-2, and the preparation method is as follows:
(1) Adding polyoxymethylene, 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 premix into a double-screw extruder from a main feeding port, adding 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-fiber-floating polyoxymethylene material. Wherein, each screw barrel temperature of twin-screw extruder from the charge door to aircraft nose is in proper order: 150-170 ℃, 160-180 ℃, 170-190 ℃, 180-200 ℃ and 180-200 ℃, the screw speed is 250-400 rpm, the feeding amount is 50-200 kg/h, and the vacuum degree is (-0.1) to 0MPa.
Comparative examples 1 to 6
Comparative examples 1 to 6 provide polyoxymethylene materials having the formulations shown in Table 2 in parts by weight, and the preparation methods were as described in examples 1 to 13.
TABLE 1
Note that: in the table "-" means that the component was not added, and the following is the same.
TABLE 2
From the test results of tables 1 to 2 above, it can be seen that: the polyoxymethylene material prepared by the embodiment of the invention has low fiber floating property, and the tensile strength reaches 86.4-128.2 MPa (the tensile strength is more than or equal to 80MPa and can meet the product requirement).
In the formula system, the addition proportion of the components can influence the tensile strength and the fiber floating condition of the material. In comparative example 5, the tensile strength of the material was significantly reduced by the addition of too little glass fiber, which was only 65.2MPa. In comparative example 6, the glass fibers were too much to be added, so that the floating fibers on the surface of the material were more and the grade 3 was achieved. Secondly, in comparative example 1, since carboxyl-terminated hyperbranched polyester was not added, the floating fiber on the surface of the material was serious, reaching grade 4. In comparative example 2, the tensile strength of the material is reduced by only 106.3MPa due to excessive carboxyl-terminated hyperbranched polyester, and the surface floating fibers are more, reaching level 3. When the material is added according to the formula of the invention, the material not only has higher tensile strength, but also has less surface floating fiber and better comprehensive performance. In sum, when 73.5 to 81 parts by weight of polyoxymethylene, 18 to 25 parts by weight of glass fiber and 0.5 to 1 part by weight of carboxyl-terminated hyperbranched polyester are used, the tensile strength of the material is higher and reaches 111.1 to 128.2MPa, and the surface floating fiber is less and reaches level 1.
It can also be seen from a comparison of examples 2 and examples 7 to 10 that the number of carboxyl groups and the molecular weight of the carboxyl-terminated hyperbranched polyester have an influence on the properties of the material, and that when the number of carboxyl groups of the carboxyl-terminated hyperbranched polyester is 12 to 24mol and the molecular weight is 2600 to 6400g/mol, the material not only has high strength but also has less surface floating fibers.
From comparative examples 3 and 4, it can be seen that the problem of surface fiber floating of POM materials is not effectively improved when hydroxyl-terminated hyperbranched polyesters or end-capped hyperbranched polyesters are used instead of carboxyl-terminated hyperbranched polyesters.
It can also be seen from comparing example 2 with examples 11 to 13 that the melt index (i.e., melt index) and weight average molecular weight of POM also affect the properties of the material, and that the material has more excellent properties when the melt index of polyoxymethylene used is 9 to 27g/10min (190 ℃ C./2.16 kg), and the weight average molecular weight is 80000 to 160000.
Finally, it should be noted that the above-mentioned embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted equally without departing from the spirit and scope of the technical solution of the present invention.
Claims (7)
1. The low-floating fiber polyformaldehyde material is characterized by comprising the following components in parts by weight: 72-89 parts of polyoxymethylene, 10-25 parts of glass fiber and 0.5-2 parts of carboxyl-terminated hyperbranched polyester;
the carboxyl number of the carboxyl-terminated hyperbranched polyester is 12-24 mol, and the molecular weight is 2600-6400 g/mol;
the melt index of the polyoxymethylene is 9-27 g/10min, the weight average molecular weight is 80000-160000, the test temperature of the melt index is 190 ℃, and the test load is 2.16kg.
2. The low-fiber polyoxymethylene material of claim 1, which comprises the following components in parts by weight: 73.5-81 parts of polyoxymethylene, 18-25 parts of glass fiber and 0.5-1 part of carboxyl-terminated hyperbranched polyester.
3. The low-fiber polyoxymethylene material as set forth in claim 1 or 2, further comprising the following components in parts by weight: 0.1-0.5 part of primary antioxidant and 0.1-0.3 part of auxiliary antioxidant, wherein the primary antioxidant is hindered phenol antioxidant, and the auxiliary antioxidant is at least one of phosphite antioxidant and thioether antioxidant.
4. A method for preparing a low-fiber polyoxymethylene material according to any one of claims 1 to 3, comprising the steps of:
uniformly mixing other components except glass fibers to obtain a premix;
and adding the premix into a double-screw extruder from a main feeding port, adding 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.
5. The method for preparing the low-fiber polyoxymethylene material according to claim 4, wherein the temperatures of each screw barrel from the feed inlet to the head of the twin-screw extruder are as follows: 150-170 ℃, 160-180 ℃, 170-190 ℃, 180-200 ℃ and 180-200 ℃, the screw speed is 250-400 rpm, the feeding amount is 50-200 kg/h, and the vacuum degree is (-0.1) to 0MPa.
6. The use of the low-fiber polyoxymethylene material according to any one of claims 1 to 3 in kitchen appliances, household appliances and automobile industry.
7. A plastic part, characterized in that it is made of a polyoxymethylene material having a low fiber content according to any one of claims 1 to 3, and is used for manufacturing kitchen appliances, home 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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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 (1)
| Title |
|---|
| 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.功能材料.2018,第49卷(第6期),第6103-6106页. * |
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