CN110229461B - TPU (thermoplastic polyurethane) in-situ polymerization toughened polyformaldehyde material and preparation method thereof - Google Patents
TPU (thermoplastic polyurethane) in-situ polymerization toughened polyformaldehyde material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of high polymer materials, and particularly relates to a TPU (thermoplastic polyurethane) in-situ polymerization toughened polyformaldehyde material and a preparation method thereof, wherein the TPU in-situ polymerization toughened polyformaldehyde material is prepared from the following raw materials in parts by weight: 50-70 parts of polyol, 0.1-2 parts of nucleating agent, 30-70 parts of isocyanate, 75-90 parts of polyformaldehyde, 0.15-0.4 part of primary antioxidant, 0.2-0.5 part of secondary antioxidant, 0.35-0.7 part of formaldehyde absorbent, 0.4-0.9 part of lubricant and 0.5-10 parts of chain extender; the invention enables the TPU to be inserted into the POM crystal region and the amorphous region in a networking structure, and the random insertion of the TPU slows down the speed of the POM molecular chain to be discharged into crystal lattices, thereby better realizing the uniform distribution and dispersion of the nucleating agent in the POM, and further realizing the great improvement of the POM toughness under the condition of ensuring the POM rigidity and strength.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a TPU (thermoplastic polyurethane) in-situ polymerization toughened polyformaldehyde material and a preparation method thereof.
Background
Polyoxymethylene (POM), also called polyoxymethylene, is a compound of-CH2O-is a high-crystallinity linear polymer with a main chain link, and the comprehensive performance is excellent. Of the five general purpose engineering plastics, the annual yields are second only to PA and PC, and occupy the third place. POM is widely used in the fields of automobiles, aerospace, electronic and electronic appliances, precision instruments and the like, particularly as parts of precision gears, bearings and the like, because of its rigidity and strength comparable to those of metals, good corrosion resistance, wear resistance, self-lubricity, and outstanding creep resistance and fatigue resistance.
However, the high crystallinity (60-80%) of POM leads to easy formation of large-size spherulites during molding, high notch sensitivity, poor toughness and low notch impact strength, which severely limits the application field of POM. Therefore, toughening modification of POMs has been one of the important research subjects in this field.
At present, toughening modification methods of POM can be mainly divided into four types: elastomer toughening modification, rigid particle toughening modification, alloying toughening modification and composite toughening agent toughening modification. The elastomer toughening modification POM is the most common toughening modification method, and the elastomer provides stress concentration points in a POM matrix to induce a large amount of silver lines and shear zones to appear, so that the matrix is promoted to generate brittle-tough transition to improve the toughness of the material. Common elastomers for toughening the modified polyoxymethylene include thermoplastic polyurethane elastomer (TPU), Ethylene Propylene Diene Monomer (EPDM), Styrene Butadiene Rubber (SBR), Nitrile Butadiene Rubber (NBR), ethylene-octene copolymer (POE), acrylate elastomers, and the like. The ultra-tough POM/PUR-T alloy developed by Du Pont company in the United states by adopting a method of mechanical blending and graft copolymerization enables the notch impact strength of the POM to be as high as 906J/m, and is improved by 17 times compared with pure POM. The rigid particle toughened POM is mainly characterized in that the crystallization behavior of the POM is changed, the spherulite structure is improved, the spherulite size is reduced, and the purpose of toughening the POM is achieved to a certain extent. The common inorganic rigid particles comprise nano calcium carbonate, silicon dioxide, glass beads, titanium dioxide, talcum powder, barium sulfate and the like, are convenient to operate and have incomparable advantages in the aspects of improving the rigidity of the POM and reducing the cost. Alloying modification is one of important means for realizing toughening modification of high polymer materials, and the POM blending alloy is prepared by blending toughness materials with excellent comprehensive performance, such as PP, LDPE, HDPE, PA and the like, with POM and additives and carrying out melt blending according to a proper proportion, and advantage complementation is realized among different materials through alloying. The composite toughening agent modified and toughened POM is also attracting more and more attention, the strength and rigidity of the POM can be improved while the toughness is improved by using rigid particles and an elastomer, and the conventional composite toughening agent mainly comprises TPU/nano particles (calcium carbonate, silicon dioxide, montmorillonite and the like), POE-g-MAH, SEBS-g-MAH, EPDM-g-MAH and the like. Melting the gold and the like by a double-screw extruderMixing method, and preparing POM/PUR-T/nano CaCO by different processing techniques3The research shows that the nano CaCO is firstly prepared3And PUR-T are premixed and extruded to prepare the composite toughening agent master batch, and then the impact toughness of the composite material prepared by pre-POM melt blending is greatly improved. Nano CaCO3The addition of the (B) enables the size of the spherulites of the POM to be reduced and the crystallinity to be reduced, thereby improving the toughness and the rigidity of the composite material to a certain degree, and when the POM/PUR-T/nano CaCO is adopted3When the mass ratio of (A) to (B) is 90:10:4, the notched impact strength of the composite material reaches 12500J/m2The composite material is improved by 135% compared with pure POM and 1.3 times compared with POM/PUR-T composite material.
Due to the particularity of the molecular structure of the POM, the compatibility of the POM and an elastic material is poor, and the ideal blending and dispersing degree is difficult to achieve, so that the impact strength of the POM and the elastic body can be improved to a certain degree only by blending; the addition of the rigid particles can increase the anisotropic nucleation points of the POM, reduce the perfect degree of spherulite growth, improve the nucleation density, improve the rigidity of the POM within a certain range, improve the toughness to a limited extent, and the uniform dispersion of the rigid particles in the POM is also a difficult problem in the industry, and the further modification of the rigid particles can further improve the production cost.
Disclosure of Invention
The invention provides a TPU in-situ polymerization toughened polyformaldehyde material and a preparation method thereof in order to solve the technical problems.
The technical scheme for solving the technical problems is as follows: the TPU in-situ polymerization toughened polyformaldehyde material is prepared from the following raw materials in parts by weight: 50-70 parts of polyol, 0.1-2 parts of nucleating agent, 30-70 parts of isocyanate, 75-90 parts of polyformaldehyde, 0.15-0.4 part of primary antioxidant, 0.2-0.5 part of secondary antioxidant, 0.35-0.7 part of formaldehyde absorbent, 0.4-0.9 part of lubricant and 0.5-10 parts of chain extender.
The invention has the beneficial effects that: the invention enables the TPU to be inserted into the POM crystal region and the amorphous region in a networking structure, and the random insertion of the TPU slows down the speed of the POM molecular chain to be discharged into crystal lattices, thereby better realizing the uniform distribution and dispersion of the nucleating agent in the POM, and further realizing the great improvement of the POM toughness under the condition of ensuring the POM rigidity and strength.
On the basis of the technical scheme, the invention can be further improved as follows.
Further preferably, the polyol is one or a mixture of more of polyester polyol (polyethylene glycol adipate glycol, polypropylene glycol adipate glycol, polybutylene glycol adipate glycol, polyhexamethylene glycol adipate glycol), polyether polyol (polyethylene glycol, polytetrahydrofuran ether glycol) and polyolefin polyol (hydroxyl-terminated polybutadiene), and the polyol is polyol with the molecular weight of 600-6000 g/mol.
As further optimization of the invention, the nucleating agent is one or a mixture of more of montmorillonite, silicon dioxide, multi-walled carbon nanotubes, calcium carbonate and glass beads, and the nucleating agent is nano-scale.
In a further preferred embodiment of the present invention, the isocyanate is one or a mixture of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate and xylylene diisocyanate.
In a further preferred embodiment of the present invention, the primary antioxidant is one or more selected from 2, 6-tertiary butyl-4-methylphenol, bis (3, 5-tertiary butyl-4-hydroxyphenyl) sulfide and tetra [ beta- (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
In a further preferred embodiment of the present invention, the secondary antioxidant is one or a mixture of more of thiodipropionate diester, didodecanolate ester, ditetradecanote ester, dioctadecyl ester, trioctyl ester, tridecyl ester, tridodecyl ester and trihexadecyl ester.
As a further preferable mode of the invention, the formaldehyde absorbent is one or a mixture of more of melamine, dicyandiamide and polyamide.
Further preferably, the lubricant is one or a mixture of several of a metal soap lubricant (zinc stearate, calcium stearate, barium stearate), a hydrocarbon wax lubricant (polyethylene wax, polypropylene wax, oxidized polyethylene wax), an amide wax (oleic acid acyl, erucamide, ethylene bis-stearic acid amide, modified EBS), and a silicone oil.
Further preferably, the chain extender is one or a mixture of more of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 2-propanediol, 1, 3-butanediol, diethylene glycol, dipropylene glycol, hydroquinone dihydroxyethyl ether and 1, 4-cyclohexanedimethanol.
The invention also provides a preparation method of the TPU in-situ polymerization toughened polyformaldehyde material, which comprises the following steps:
A. weighing the following raw materials in parts by weight: 50-70 parts of polyol, 0.1-2 parts of nucleating agent, 30-70 parts of isocyanate, 75-90 parts of polyformaldehyde, 0.15-0.4 part of primary antioxidant, 0.2-0.5 part of secondary antioxidant, 0.35-0.7 part of formaldehyde absorbent, 0.4-0.9 part of lubricant and 0.5-10 parts of chain extender;
B. mixing polyol and nucleating agent uniformly, and then adding isocyanate to obtain prepolymer for later use;
C. uniformly mixing polyformaldehyde, a main antioxidant, an auxiliary antioxidant, a formaldehyde absorbent, a lubricant and a chain extender, and reacting to obtain a blend melt;
D. and C, blending the prepolymer obtained in the step B and the blend melt obtained in the step C for reaction to obtain the TPU in-situ polymerization toughened polyformaldehyde material.
The preparation method has simple and easy process, and solves the problems of compatibility of TPU and POM and uniform dispersion of nucleating agent in POM melt.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1
A. Weighing the following raw materials in parts by weight: 50kg of polytetrahydrofuran ether glycol (Mn ═ 2000), 0.5kg of nano-silica, 30kg of 4, 4' -diphenylmethane diisocyanate, 90kg of polyformaldehyde, 0.2kg of 2, 6-tertiary butyl-4-methylphenol, 0.2kg of didodecyl alcohol ester, 0.35kg of dicyandiamide, 0.4kg of polyethylene wax and 0.5kg of 1, 4-butanediol;
B. adding polytetrahydrofuran ether glycol (Mn ═ 2000) and nano silicon dioxide into a reaction kettle, uniformly mixing to obtain a blend, then adding the blend and 4, 4' -diphenylmethane diisocyanate into a co-rotating double-screw extruder, and co-mixing and extruding to obtain a prepolymer for later use; wherein the temperature from the feed inlet to the neck ring of the co-rotating twin-screw extruder is set to 110 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃ and the rotating speed of the main machine is 210 rpm;
C. uniformly mixing polyformaldehyde, 2, 6-tertiary butyl-4-methylphenol, behenyl ester, dicyandiamide, polyethylene wax and 1, 4-butanediol, adding the mixture into a co-rotating double-screw extruder, and reacting to obtain a blend melt; wherein the temperature from the feed inlet of the co-rotating twin-screw extruder to the neck mold is set to be 110 ℃, 150 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃ and the rotating speed of the main machine is 200 rpm;
D. adding the prepolymer obtained in the step B and the blend melt obtained in the step C into a co-rotating double-screw extruder, wherein the temperature from a feed inlet of the co-rotating double-screw extruder to a neck mold is set to be 190 ℃, 200 ℃, 210 ℃, 170 ℃, 150 ℃, 100 ℃ and 100 ℃, and the rotating speed of a main machine is 200 rpm; and then cooling, granulating and drying to obtain the TPU in-situ polymerization toughened polyformaldehyde material.
Example 2
The preparation method is as in example 1, and the mechanical properties of the material are shown in Table 1 below.
Example 3
| Raw materials | Weight (D) |
| Polyoxymethylene | 80kg |
| 2, 6-Tertiary butyl-4-methylphenol | 0.2kg |
| Docosanol ester | 0.2kg |
| Dicyandiamide | 0.35kg |
| Polyethylene wax | 0.4kg |
| Nano silicon dioxide | 0.5kg |
| Polyethylene glycol adipate glycol (Mn ═ 2000) | 70kg |
| 4, 4' -diphenylmethane diisocyanate | 40kg |
| 1, 3-propanediol | 8kg |
The preparation method is as in example 1, and the mechanical properties of the material are shown in Table 1 below.
Comparative example 1
| Raw materials | Weight (D) |
| Polyoxymethylene | 100kg |
| 2, 6-Tertiary butyl-4-methylphenol | 0.2kg |
| Docosanol ester | 0.2kg |
| Dicyandiamide | 0.35kg |
| Polyethylene wax | 0.4kg |
The preparation method is as in example 1, and the mechanical properties of the material are shown in Table 1 below.
Comparative example 2
| Raw materials | Weight (D) |
| Polyoxymethylene | 100kg |
| 2, 6-Tertiary butyl-4-methylphenol | 0.2kg |
| Docosanol ester | 0.2kg |
| Dicyandiamide | 0.35kg |
| Polyethylene wax | 0.4kg |
| Nano silicon dioxide | 0.5kg |
The preparation method is as in example 1, and the mechanical properties of the material are shown in Table 1 below.
TABLE 1
The evaluation criteria for the mechanical properties of the materials are as follows:
(1) tensile strength and elongation at break: measured according to ASTM D638;
(2) flexural strength and flexural modulus: measured according to ASTM D790;
(3) impact strength of the simply supported beam notch: measured according to ASTM D6110.
As can be seen from Table 1, the addition of the nucleating agent in comparative example 2 resulted in a POM notched impact strength of from 6kJ/m, as compared with that of POM in comparative example 12Increase to 8kJ/m2The tensile strength was also improved, whereas the notched impact strength in example 1 was improved by 150% compared to comparative example 1, the tensile strength was also significantly improved, and the notched impact strength was reduced after the use of the polyester TPU, but with the amount of TPU usedThe increase in notched impact strength is significant, but too high a level may affect tensile strength. As can be seen from the comparison of all data, the TPU in-situ polymerization toughened polyformaldehyde has obvious feasibility, and the toughness of the POM can be greatly improved on the basis of ensuring the strength of the POM.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. The TPU in-situ polymerization toughened polyformaldehyde material is characterized by being prepared from the following raw materials in parts by weight: 50-70 parts of polyol, 0.1-2 parts of nucleating agent, 30-70 parts of isocyanate, 75-90 parts of polyformaldehyde, 0.15-0.4 part of primary antioxidant, 0.2-0.5 part of auxiliary antioxidant, 0.35-0.7 part of formaldehyde absorbent, 0.4-0.9 part of lubricant and 0.5-10 parts of chain extender, wherein the preparation method of the TPU in-situ polymerization toughened polyformaldehyde material comprises the following steps:
A. weighing the following raw materials in parts by weight: 50-70 parts of polyol, 0.1-2 parts of nucleating agent, 30-70 parts of isocyanate, 75-90 parts of polyformaldehyde, 0.15-0.4 part of primary antioxidant, 0.2-0.5 part of secondary antioxidant, 0.35-0.7 part of formaldehyde absorbent, 0.4-0.9 part of lubricant and 0.5-10 parts of chain extender;
B. mixing polyol and nucleating agent uniformly, and then adding isocyanate to obtain prepolymer for later use;
C. uniformly mixing polyformaldehyde, a main antioxidant, an auxiliary antioxidant, a formaldehyde absorbent, a lubricant and a chain extender, and reacting to obtain a blend melt;
D. and C, blending the prepolymer obtained in the step B and the blend melt obtained in the step C for reaction to obtain the TPU in-situ polymerization toughened polyformaldehyde material.
2. The TPU in-situ polymerization toughened polyformaldehyde material as claimed in claim 1, wherein the polyol is one or more of polyester polyol, polyether polyol and polyolefin polyol.
3. The TPU in-situ polymerization toughened polyformaldehyde material as claimed in claim 1, wherein the nucleating agent is one or more of montmorillonite, silica, multi-walled carbon nanotube, calcium carbonate and glass microsphere.
4. The TPU in-situ polymerized toughened polyformaldehyde material of claim 1, wherein the isocyanate is one or more selected from the group consisting of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate and xylylene diisocyanate.
5. The TPU in-situ polymerization toughened polyformaldehyde material as claimed in claim 1, wherein the primary antioxidant is one or more selected from 2, 6-tertiary butyl-4-methylphenol, bis (3, 5-tertiary butyl-4-hydroxyphenyl) sulfide and tetra [ β - (3, 5-tertiary butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester.
6. The TPU in-situ polymerized toughened polyformaldehyde material as claimed in claim 1, wherein the secondary antioxidant is one or more selected from the group consisting of diester thiodipropionate, didodecyl alcohol ester, ditetradecyl alcohol ester, dioctadecyl alcohol ester, trioctyl ester, tridecyl ester, tridodecyl alcohol ester and trihexadecyl alcohol ester.
7. The TPU in-situ polymerized toughened polyformaldehyde material as claimed in claim 1, wherein the formaldehyde absorbent is one or more of melamine, dicyandiamide and polyamide.
8. The TPU in-situ polymerized toughened polyformaldehyde material as claimed in claim 1, wherein the lubricant is one or more of metal soap lubricant, hydrocarbon wax lubricant, amide wax and silicone oil.
9. The TPU in-situ polymerization toughened polyformaldehyde material as claimed in claim 1, wherein the chain extender is one or more of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 2-propanediol, 1, 3-butanediol, diethylene glycol, dipropylene glycol, hydroquinone bis hydroxyethyl ether and 1, 4-cyclohexanedimethanol.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558754A (en) * | 2011-12-23 | 2012-07-11 | 四川大学 | Chain-extended modified and copolymerized formaldehyde resin and preparation method thereof |
| CN105131511A (en) * | 2015-08-31 | 2015-12-09 | 宁波海雨新材料科技有限公司 | Low-temperature toughened polyformaldehyde composite material and preparing method thereof |
| CN109181279A (en) * | 2018-07-20 | 2019-01-11 | 山东诺威聚氨酯股份有限公司 | Heat-conduction polyurethane elastomer and preparation method thereof for mobile phone protective cover |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558754A (en) * | 2011-12-23 | 2012-07-11 | 四川大学 | Chain-extended modified and copolymerized formaldehyde resin and preparation method thereof |
| CN105131511A (en) * | 2015-08-31 | 2015-12-09 | 宁波海雨新材料科技有限公司 | Low-temperature toughened polyformaldehyde composite material and preparing method thereof |
| CN109181279A (en) * | 2018-07-20 | 2019-01-11 | 山东诺威聚氨酯股份有限公司 | Heat-conduction polyurethane elastomer and preparation method thereof for mobile phone protective cover |
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