CN110229461A - A kind of TPU in-situ polymerization reinforced polyformaldehyde materials and preparation method thereof - Google Patents
A kind of TPU in-situ polymerization reinforced polyformaldehyde materials and preparation method thereof Download PDFInfo
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- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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Abstract
The invention belongs to technical field of polymer materials, more particularly to a kind of TPU in-situ polymerization reinforced polyformaldehyde materials and preparation method thereof, the TPU in-situ polymerization reinforced polyformaldehyde materials, are made of raw material from the following weight: 50-70 parts of polyalcohol, 0.1-2 parts of nucleating agent, 30-70 parts of isocyanates, 75-90 parts of polyformaldehyde, 0.15-0.4 parts of main anti-oxidant, antioxidant 0.2-0.5 parts auxiliary, 0.35-0.7 parts of formaldehyde absorbent, 0.4-0.9 parts and chain extender 0.5-10 parts of lubricant；The present invention is interspersed in TPU in the crystalline region POM and amorphous area with network structure, random due to TPU interts, slow down the speed that POM strand is discharged into lattice, it is uniformly distributed dispersion in POM to which nucleating agent be better achieved, to realize increasing substantially for POM toughness in the case where guaranteeing POM stiffness and strength.
Description
Technical field
The invention belongs to technical field of polymer materials more particularly to a kind of TPU in-situ polymerization reinforced polyformaldehyde materials and
Preparation method.
Background technique
Polyformaldehyde (POM), is called polyoxymethylene, is one kind with-CH2O- is the high-crystallinity linear polymerization of main chain chain link
Object, excellent combination property.In five big general engineering plastics, annual output is only second to PA and PC, occupies third position.POM is because of it
Match in excellence or beauty the rigidity and intensity of metal, good corrosion resistance, wearability, self-lubrication and creep resistant outstanding, endurance
Property and be widely used in the fields such as automobile, aerospace, electronic apparatus, precision instrument, be especially used as the portions such as precision gear, bearing
Part.
However POM high-crystallinity (60%-80%), large scale spherocrystal easy to form during causing it to form, notch sensitive
Big, the poor toughness of property, notch impact strength is low, seriously limits the application field of POM.Therefore, toughening modifying is carried out always to POM
It is one of the important subject in the field.
Currently, the toughening modifying method of POM can be divided mainly into four classes: elastic body toughening is modified, Rigid Particles Toughened is modified,
Alloying toughening modifying and composite toughing agent toughening modifying.Wherein the modified POM of elastic body toughening is that the most commonly used toughening changes
Property method, stress concentration point is provided in POM matrix by elastomer, inducing a large amount of crazings and shear band occurs, and promotes matrix
Brittle-tough transition occurs to improve the toughness of material.The elastomer of common polyacetal includes thermoplastic polyurethane bullet
Property body (TPU), ethylene propylene diene rubber (EPDM), butadiene-styrene rubber (SBR), nitrile rubber (NBR), ethylene-octene copolymer
(POE), acrylic ester elastomer etc..Du Pont company, the U.S. is developed using mechanical blending and the method for graft copolymerization
Ultra-toughness POM/PUR-T alloy improve 17 times than pure POM so that the notch impact strength of POM is up to 906J/m.Rigid grain
Sub- toughening POM is mainly to pass through the crystallization behavior for changing POM, improves spherulitic crystal structure, spherulite size is made to become smaller, to a certain extent
Achieve the purpose that toughening POM.Common inorganic rigid particle includes nanometer grade calcium carbonate, silica, glass microballoon, titanium dioxide
Titanium, talcum powder, barium sulfate etc., it is easy to operate, there is unrivaled advantage improving POM rigidity, dropping low cost aspect.Alloying
Modification is to realize one of the important means of high molecular material toughening modifying, by the toughness material of high comprehensive performance, as PP,
LDPE, HDPE, PA etc. are blended with POM, additive, carry out melt blending by appropriate proportion and POM blend alloy is made, pass through conjunction
Aurification to realize have complementary advantages between different materials.And the modified toughened POM of composite toughing agent is equally increasingly concerned by people, and passes through
Rigid particles are used in combination with elastomer, can also improve its intensity and rigidity, present composite toughing agent master while improving POM toughness
It to include TPU/ nanoparticle (calcium carbonate, silica, montmorillonite etc.), POE-g-MAH, SEBS-g-MAH, EPDM-g-MAH
Etc..Jin Lu etc. uses double screw extruder melt-blending process, is prepared for POM/PUR-T/ Nano-meter CaCO3 with different processing technologys3
Composite material, research are found Nano-meter CaCO3 first3It is squeezed out with PUR-T premixing and composite toughing agent master batch is made, then pre- POM is molten
Melt blending composite impact toughness obtained to be greatly improved.Nano-meter CaCO33Be added so that the spherulite size of POM subtracts
Small, crystallinity reduces, so that the toughness of composite material and rigidity obtain a degree of raising, and works as POM/PUR-
T/ Nano-meter CaCO33Mass ratio be 90:10:4 when, the notch impact strength of composite material reaches 12500J/m2, improved than pure POM
135%, than year-on-year POM/PUR-T composite material improve 1.3 times.
It is poor with the compatibility of elastic material due to the particularity of POM molecular structure, it is difficult to reach ideal be blended and divide
The degree of dissipating, so POM can only improve its impact strength with elastomer blended to a certain extent；The addition of rigid particles can increase
Add the incorgruous nucleating point of POM, reduce spherulitic growth degree of perfection, improves nucleation density, the rigid of POM can be improved in a certain range
Property, toughness improves limited, and evenly dispersed in POM of rigid particles is equally industry problem, to rigid particles into one
Step modification will be so that production cost further increases.
Summary of the invention
In order to solve the above-mentioned technical problem the present invention provides a kind of TPU in-situ polymerization reinforced polyformaldehyde materials and its preparation side
Method.
The technical scheme to solve the above technical problems is that a kind of TPU in-situ polymerization reinforced polyformaldehyde materials, by
The raw material of following parts by weight is made: 50-70 parts of polyalcohol, 0.1-2 parts of nucleating agent, 30-70 parts of isocyanates, polyformaldehyde 75-90
Part, 0.15-0.4 parts of main anti-oxidant, antioxidant 0.2-0.5 parts auxiliary, 0.35-0.7 parts of formaldehyde absorbent, lubricant 0.4-
0.9 part and chain extender 0.5-10 parts.
The beneficial effects of the present invention are: the present invention is interspersed in TPU in the crystalline region POM and amorphous area with network structure, by
In the random interspersed of TPU, the speed that POM strand is discharged into lattice is slowed down, so that nucleating agent be better achieved in POM
It is uniformly distributed dispersion, to realize increasing substantially for POM toughness in the case where guaranteeing POM stiffness and strength.
Based on the above technical solution, the present invention can also be improved as follows.
Further preferably as the present invention, the polyalcohol is that (polyethylene glycol adipate glycol gathers oneself to polyester polyol
Two acid propylene glycol ester glycol, polybutylene glyool adipate, polyhexamethylene adipate glycol), polyether polyol (poly- second two
Alcohol, polytetrahydrofuran ether glycol) mixture with one or more of polyolefin polyhydric alcohol (end hydroxy butadiene), it is described
Polyalcohol is polyalcohol of the molecular weight in 600-6000g/mol.
Further preferably as the present invention, the nucleating agent is montmorillonite, silica, multi-walled carbon nanotube, calcium carbonate
With the mixture of one or more of glass microballoon, which is nanoscale.
Further preferably as the present invention, the isocyanates is toluene di-isocyanate(TDI), diphenylmethane diisocyanate
Ester, hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, isophorone diisocyanate and phenylenedimethylidyne two
The mixture of one or more of isocyanates.
Further preferably as the present invention, the main anti-oxidant is 2,6- three-level butyl -4- methylphenol, bis- (3,5-
Three-level butyl -4- hydroxy phenyl) in thioether and four [β-(3,5- three-level butyl -4- hydroxy phenyl) propionic acid] pentaerythritol esters one
Kind or several mixtures.
Further preferably as the present invention, the auxiliary anti-oxidant is thio-2 acid dibasic acid esters, double Lauryl Alcohol esters, double 14
Carbon alcohol ester, double octadecanol esters, three monooctyl esters, three last of the ten Heavenly stems esters and one of three (Lauryl Alcohol) esters and three (16 carbon alcohol) esters or several
The mixture of kind.
Further preferably as the present invention, the formaldehyde absorbent is one of melamine, dicyandiamide and polyamide
Or several mixture.
As it is of the invention further preferably, the lubricant is that metal soap lubricant is (zinc stearate, calcium stearate, hard
Resin acid barium), chloroflo series lubricant agent (polyethylene wax, polypropylene wax, oxidized polyethylene wax), amide waxe (oleic acid acid acyl, erucic acid acyl
Amine, ethylenebis stearic amide, modified EBS), the mixture of one or more of organic silicone oil.
Further preferably as the present invention, the chain extender is ethylene glycol, 1,3-PD, 1,4-butanediol, 1,5- penta
Glycol, 1,6- hexylene glycol, 1,2-PD, 1,3-BDO, diethylene glycol, dipropylene glycol, hydroquinone two hydroxy ethyl ether with
The mixture of one or more of 1,4 cyclohexane dimethanol.
The present invention also provides a kind of preparation methods of TPU in-situ polymerization reinforced polyformaldehyde materials, comprising the following steps:
A, weigh raw material by following parts by weight: 50-70 portions of polyalcohol, 30-70 parts of isocyanates, gathers 0.1-2 parts of nucleating agent
75-90 parts of formaldehyde, 0.15-0.4 parts of main anti-oxidant, antioxidant 0.2-0.5 parts auxiliary, 0.35-0.7 parts of formaldehyde absorbent, profit
0.4-0.9 parts and chain extender 0.5-10 parts of lubrication prescription；
B, polyalcohol and nucleating agent are mixed, isocyanates is then added, obtains prepolymer, it is spare；
C, polyformaldehyde, main anti-oxidant, auxiliary antioxidant, formaldehyde absorbent, lubricant and chain extender are mixed, is reacted
To blend melt；
D, by the prepolymer that step B is obtained and the blend melt blending reaction that step C is obtained to get TPU in-situ polymerization
Reinforced polyformaldehyde materials.
Its is simple for process for preparation method of the present invention, and the consistency problem and nucleating agent for solving TPU and POM exist
Evenly dispersed problem in POM melt.
Specific embodiment
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit
Determine the scope of the present invention.
Embodiment 1
A, raw material is weighed by following weight: polytetrahydrofuran ether glycol (Mn=2000) 50kg, nano silica
0.5kg, 4,4`- methyl diphenylene diisocyanate 30kg, polyformaldehyde 90kg, 2,6- three-level butyl -4- methylphenol 0.2kg,
Double Lauryl Alcohol ester 0.2kg, dicyandiamide 0.35kg, polyethylene wax 0.4kg and 1,4-butanediol 0.5kg；
B, polytetrahydrofuran ether glycol (Mn=2000) and nano silica are added in reaction kettle and are mixed, is blended
Object, then by blend and 4,4`- methyl diphenylene diisocyanate is added blending extrusion in parallel dual-screw extruding machine, obtains
Prepolymer, it is spare；It is wherein 110 DEG C, 170 DEG C, 180 to the temperature setting of mouth mold from the feed opening of parallel dual-screw extruding machine
DEG C, 190 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, 200 DEG C, engine speed 210rpm；
C, by polyformaldehyde, 2,6- three-level butyl -4- methylphenol, double Lauryl Alcohol esters, dicyandiamide, polyethylene wax and Isosorbide-5-Nitrae -
Butanediol, which mixes, is added parallel dual-screw extruding machine, and reaction obtains blend melt；Wherein parallel dual-screw extruding machine feed opening
Temperature setting to mouth mold is 110 DEG C, 150 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, 210 DEG C, host
Revolving speed is 200rpm；
D, parallel dual-screw extruding machine is added in the prepolymer that step B is obtained and the blend melt that step C is obtained, wherein
Parallel dual-screw extruding machine feed opening to mouth mold temperature setting be 190 DEG C, 200 DEG C, 210 DEG C, 210 DEG C, 170 DEG C, 150 DEG C,
100 DEG C, 100 DEG C, 100 DEG C, engine speed 200rpm；Then by cooling, granulation, drying to get TPU in-situ polymerization toughening
Polyformaldehyde material.
Embodiment 2
Preparation method process such as embodiment 1, the mechanical property of material see the table below 1.
Embodiment 3
| Raw material | Weight |
| Polyformaldehyde | 80kg |
| 2,6- three-level butyl -4- methylphenols | 0.2kg |
| Double Lauryl Alcohol esters | 0.2kg |
| Dicyandiamide | 0.35kg |
| Polyethylene wax | 0.4kg |
| Nano silica | 0.5kg |
| Polyethylene glycol adipate glycol (Mn=2000) | 70kg |
| 4,4`- methyl diphenylene diisocyanates | 40kg |
| 1,3- propylene glycol | 8kg |
Preparation method process such as embodiment 1, the mechanical property of material see the table below 1.
Comparative example 1
| Raw material | Weight |
| Polyformaldehyde | 100kg |
| 2,6- three-level butyl -4- methylphenols | 0.2kg |
| Double Lauryl Alcohol esters | 0.2kg |
| Dicyandiamide | 0.35kg |
| Polyethylene wax | 0.4kg |
Preparation method process such as embodiment 1, the mechanical property of material see the table below 1.
Comparative example 2
| Raw material | Weight |
| Polyformaldehyde | 100kg |
| 2,6- three-level butyl -4- methylphenols | 0.2kg |
| Double Lauryl Alcohol esters | 0.2kg |
| Dicyandiamide | 0.35kg |
| Polyethylene wax | 0.4kg |
| Nano silica | 0.5kg |
Preparation method process such as embodiment 1, the mechanical property of material see the table below 1.
Table 1
It is as follows to the mechanical property evaluation criteria of material:
(1) it tensile strength and elongation at break: is measured according to ASTM D638；
(2) it bending strength and bending modulus: is measured according to ASTM D790；
(3) it simply supported beam notch impact strength: is measured according to ASTM D6110.
It can be seen from Table 1 that compared to the POM in comparative example 1, nucleating agent is added in comparative example 2, so that POM notch
Impact strength is by 6kJ/m2Rise to 8kJ/m2, tensile strength also increases, and notch impact strength relatively compares in embodiment 1
Example 1 improves 150%, and tensile strength also significantly improves, and notch impact strength after polyester-type TPU is used to decrease, but with
The increase of TPU dosage, notch impact strength significantly improve, but too high dosage will affect tensile strength.With regard to total data pair
Than can be seen that TPU in-situ polymerization reinforced polyformaldehyde with obvious feasibility, can significantly be mentioned on the basis of guaranteeing POM intensity
The toughness of high POM.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all in spirit of the invention and
Within principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of TPU in-situ polymerization reinforced polyformaldehyde materials, which is characterized in that be made of raw material from the following weight: polyalcohol
50-70 parts, it is 0.1-2 parts of nucleating agent, 30-70 parts of isocyanates, 75-90 parts of polyformaldehyde, 0.15-0.4 parts of main anti-oxidant, auxiliary anti-
0.2-0.5 parts of oxidant, 0.35-0.7 parts of formaldehyde absorbent, 0.4-0.9 parts and chain extender 0.5-10 parts of lubricant.
2. a kind of TPU in-situ polymerization reinforced polyformaldehyde materials according to claim 1, which is characterized in that the polyalcohol is
The mixture of one or more of polyester polyol, polyether polyol and polyolefin polyhydric alcohol.
3. a kind of TPU in-situ polymerization reinforced polyformaldehyde materials according to claim 1, which is characterized in that the nucleating agent is
The mixture of one or more of montmorillonite, silica, multi-walled carbon nanotube, calcium carbonate and glass microballoon.
4. a kind of TPU in-situ polymerization reinforced polyformaldehyde materials according to claim 1, which is characterized in that the isocyanates
For toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate
The mixture of one or more of ester, isophorone diisocyanate and benzene dimethylene diisocyanate.
5. a kind of TPU in-situ polymerization reinforced polyformaldehyde materials according to claim 1, which is characterized in that the master is anti-oxidant
Agent is 2,6- three-level butyl -4- methylphenol, bis- (3,5- three-level butyl -4- hydroxy phenyl) thioethers and four [β-(3,5- three-level fourths
Base -4- hydroxy phenyl) propionic acid] one or more of pentaerythritol ester mixture.
6. a kind of TPU in-situ polymerization reinforced polyformaldehyde materials according to claim 1, which is characterized in that the auxiliary anti-oxidant
For thio-2 acid dibasic acid esters, double Lauryl Alcohol esters, bi-myristoleyl, double octadecanol esters, three monooctyl esters, three last of the ten Heavenly stems esters, three (12
Carbon alcohol) one or more of ester and three (16 carbon alcohol) esters mixture.
7. a kind of TPU in-situ polymerization reinforced polyformaldehyde materials according to claim 1, which is characterized in that the formaldehyde absorption
Agent is the mixture of one or more of melamine, dicyandiamide and polyamide.
8. a kind of TPU in-situ polymerization reinforced polyformaldehyde materials according to claim 1, which is characterized in that the lubricant is
The mixture of one or more of metal soap lubricant, chloroflo series lubricant agent, amide waxe and organic silicone oil.
9. a kind of TPU in-situ polymerization reinforced polyformaldehyde materials according to claim 1, which is characterized in that the chain extender is
Ethylene glycol, 1,3-PD, 1,4-butanediol, 1,5-PD, 1,6- hexylene glycol, 1,2-PD, 1,3-BDO, diethyl
The mixture of one or more of glycol, dipropylene glycol, hydroquinone two hydroxy ethyl ether and 1,4 cyclohexane dimethanol.
10. a kind of preparation method of TPU in-situ polymerization reinforced polyformaldehyde materials, which comprises the following steps:
A, raw material is weighed by following parts by weight: 50-70 parts of polyalcohol, 0.1-2 parts of nucleating agent, 30-70 parts of isocyanates, polyformaldehyde
75-90 parts, 0.15-0.4 parts of main anti-oxidant, antioxidant 0.2-0.5 parts auxiliary, 0.35-0.7 parts of formaldehyde absorbent, lubricant
0.4-0.9 parts and chain extender 0.5-10 parts；
B, polyalcohol and nucleating agent are mixed, isocyanates is then added, obtains prepolymer, it is spare；
C, polyformaldehyde, main anti-oxidant, auxiliary antioxidant, formaldehyde absorbent, lubricant and chain extender are mixed, reaction is total to
Mixed object melt；
D, by the prepolymer that step B is obtained and the blend melt blending reaction that step C is obtained to get TPU in-situ polymerization toughening
Polyformaldehyde material.
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| CN114276648A (en) * | 2021-12-03 | 2022-04-05 | 深圳市众德祥科技有限公司 | Binder, crystal refined injection molding feed and preparation method thereof |
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