CN106987114A - A kind of preparation for the composite assistant being modified for thermoplastic polyurethane - Google Patents
A kind of preparation for the composite assistant being modified for thermoplastic polyurethane Download PDFInfo
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- CN106987114A CN106987114A CN201710290868.3A CN201710290868A CN106987114A CN 106987114 A CN106987114 A CN 106987114A CN 201710290868 A CN201710290868 A CN 201710290868A CN 106987114 A CN106987114 A CN 106987114A
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- thermoplastic polyurethane
- composite
- composite assistant
- antioxidant
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3472—Five-membered rings
- C08K5/3475—Five-membered rings condensed with carbocyclic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/10—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses the preparation method for the composite assistant being modified for thermoplastic polyurethane, the composite assistant contains in the composite of 100 parts of mass fraction, including 36 parts of ultra-violet absorbers, 30 40 parts of antioxidant, 36 parts of crosslinking agents, 50 60 parts of needle shape wollastonite powders, wherein described ultra-violet absorber is benzotriazole or triazines, antioxidant is alkoxide or Polyphenols and phosphoric acid ester, crosslinking agent is oxazoline class, and needle shape wollastonite powder is the natural acicular wollastonite powder Jing Guo coupling agent treatment.By the blended composite for obtaining can be used for thermoplastic polyurethane modification of above-mentioned material, this composite not only ensures that thermoplastic polyurethane has anti-oxidant and anti-light aging performance, thermoplastic polyurethane relative molecular weight can be improved again, the toughness of product is improved, the rigidity of thermoplastic polyurethane can be also improved.
Description
Technical field
The invention belongs to high polymer material auxiliary agent technical field, it is related to compound in a kind of modification for thermoplastic polyurethane
The preparation method of auxiliary agent, the composite assistant be applicable to polyurethane, thermoplastic polyurethane, polyester, makrolon, polystyrene and
The polymer such as polyolefin masterbatch, present invention is mainly applied to thermoplastic polyurethane technical field of modification.
Background technology
Polyurethane (abbreviation PU) is polynary by polyisocyanates and PPG or PEPA and/or small molecule
The polymer that the raw material such as the crosslinking agents such as alcohol, polyamine or water or crosslinking agent is made；Pass through feed change species and composition, Ke Yi great
Change to amplitude product form and its performance, obtain from softness to hard final products；Polyurethane product form have it is soft, half
Hard and rigid foam, elastomer, paint, adhesive, fluid sealant, synthetic leather coating resin, elastomer etc., extensively
It is general to be applied to automobile making, refrigerator manufacture, communications and transportation, civil construction, footwear, synthetic leather, fabric, electromechanics, petrochemical industry, ore deposit
Many fields such as mountain machinery, aviation, medical treatment, agricultural.
Thermoplastic polyurethane (abbreviation TPU) is because elastic good, physical property is good, various mechanical strengths are all fine, therefore, extensively
For projecting, extrusion, roll and be dissolved into the processing modes such as solution resin, be the plastic cement material that plastic cement processer is commonly used
Material, the scope that product covers commercial Application and civilian necessity is made in it.In recent years, because new product is constantly developed, heat
The consumption of plasticity PU elastomers just constantly increase in, be plastic cement processer start low cost, high additive value industry it is new
Opportunity.Thermoplastic polyurethane (abbreviation TPU) is increasingly subject to the welcome of people because of its superior performance and environmentally friendly concept.TPU is not only
Possess the high-tension, high-tensile strength, tough and ageing-resistant characteristic of brilliance, and be kind of a ripe environment-friendly materials.Thermoplastic poly ammonia
The main function that composite assistant in ester modified is modified is：Improve the mechanical property and ageing resistance of thermoplastic polyurethane product
Energy；Improve the functional strength of thermoplastic polyurethane product, play reinforcement, humidification；Improve the dimensional stability of product；Adjustment heat
The rheological property of plastic polyurethane.The present invention introduces ultra-violet absorber, crosslinking agent, and antioxidant, needle shape wollastonite powder passes through
Performance test, is significantly better than the effect of current single formula, achieves good effect, and to the application of thermoplastic polyurethane
Serve facilitation.Composite assistant in being modified using thermoplastic polyurethane, can not only improve thermoplastic polyurethane rigid
Meanwhile, thermoplastic polyurethane relative molecular weight can be improved again, ensure that thermoplastic polyurethane has higher toughness and anti-oxidant again
With anti-light aging performance.
The content of the invention
It is an object of the invention to provide a kind of composite assistant for thermoplastic polyurethane, it makes an addition to thermoplastic poly ammonia
The rigidity, toughness, anti-oxidant and anti-light aging performance of product can be significantly improved in ester；It is a further object of the present invention to provide for
The preparation method of the composite assistant of thermoplastic polyurethane.
The present invention is for the ultra-violet absorber containing 3-6 parts of mass fraction in the composite assistant of thermoplastic polyurethane, such as
Benzotriazole Ultraviolet Stabilizer：2- (2'- hydroxyl -3'- tertiary butyl -5'- aminomethyl phenyls) -5- chlorobenzotriazoles or 2- (2-
Hydroxyl -3,5- di-tert-pentyl-phenyls) BTA；Such as triazine-based ultraviolet absorbent：2- (double (the 2,4- dimethyl benzenes of 4,6-
Base) -1,3,5- triazine -2- bases) -5- octyloxies phenol or 2-（4,6- diphenyl -1,3,5-triazines -2）- 5- n-hexane epoxide benzene
Phenol.Ultra-violet absorber is current most popular light stabilizer, and it can absorb ultraviolet luminous energy, and by energy with heat energy and nothing
Harmful Low emissivity can be consumed, so as to delay the photooxidation of high polymer material, improve the light resistance of material.
The present invention is for the antioxidant containing 30-40 parts of mass fraction in the composite assistant of thermoplastic polyurethane, such as:
β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid or four [β-（3,5- di-t-butyl 4- hydroxy phenyls）Third
Acid] pentaerythritol ester or N, N '-bis- [β-(3,5- di-tert-butyl-hydroxy phenyl) propionyl] hydrazines, three [2.4- di-tert-butyls
Base] phosphite ester；Main purpose is to reduce the oxidative degradation of thermoplastic polyurethane process and product, extends making for product
Use the time.
The present invention in the composite assistant of thermoplastic polyurethane for containing 3-6 parts of crosslinking agents of mass fraction：Ru oxazoline classes：
1,3-, phenyl-bis- (bisoxazolines）Or Isosorbide-5-Nitrae-, phenyl-bis- (bisoxazolines）Or double (bisoxazolines）.Crosslinking agent is typically one
Plant bifunctional compound, the radical reaction of very easy similar polymers chain end；Chain extending reaction is typically referred to using crosslinking agent etc.
Means, pass through the group with some polymer in a short time（Generally in end）It is connected and increases polymer average molecular matter
The reaction of amount；Popular response, especially polycondensation reaction, after the reaction the phase slough small molecule（Such as water）Difficulty, polymer is sometimes up to
Less than required relative molecular mass.
It is troublesome poeration, time-consuming, uneconomical although using solid phase high relative molecular mass can be obtained.Therefore, make
One of important method to improve relative molecular mass is, it is necessary to which application is quick, can effectively, on extruder be completed in several minutes
The chain extending reaction of extrusion；At present, application of the chain extending reaction in synthesis of polymer material is increasingly extensive.Oxazoline class crosslinking agent pair
Thermoplastic polyurethane carries out chain extension thickening, inherent viscosity can be made substantially to increase, and melt index declines, content of carboxyl end group reduction, end
Amino content is constant, and normal temperature notch impact strength has clear improvement, and thermoplastic polyurethane can meet wanting for extrusion grade after chain extension
Ask, its technique is easy to apply in production.
The present invention is for the needle shape wollastonite powder containing 50-60 parts of mass fraction in the composite assistant of thermoplastic polyurethane.
Natural acicular wollastonite is used, particle diameter is 2000 mesh to 3000 mesh, and its powder structure is needle-like, and draw ratio is (15-20):
1, it is more common material, acicular wollastonite is after coupling agent is surface-treated, because coupling agent one end is with high living
Property the hydroxyl on Gong Nengtuan and wollastonite surface act on, be connected to filler surface；The longer flexible chain of its other end is then covered in
The surface of polymer, forms flexible interface layer；This structure is conducive to the impact strength for improving compound to substantially improve
Its with polymer base material interface binding power, so as to improve the load and ability to bear of composite.
By above-mentioned component in following ratio (mass fraction)：3-6 parts of ultra-violet absorber；30-40 parts of antioxidant；Crosslinking
3-6 parts of agent；After the raw material that 50-60 parts of needle shape wollastonite powder is sufficiently mixed uniformly in high mixer, you can obtain being used for thermoplasticity
Polyurethane-modified composite assistant.Operation is simple for this method, and cost is low.
Composite assistant during the present invention is modified for thermoplastic polyurethane possesses following performance：
（1）Possess good toughness, antioxygenic property and prevent product light degradation etc.；
（2）Must have big draw ratio and enough intensity and toughness, possess good effect to the enhancing of plastics；
（3）With the adhesion and compatibility with polymer, have than relatively low density, the tensile strength and elasticity of product can be increased
Rate, increases the bending strength of material；
（4）Improve impact strength and case hardness increase；
（5）It is nontoxic, odorless, pollution-free and cheap.
Being mainly technically characterized by thermoplastic polyurethane modified system of the present invention introduces ultra-violet absorber and anti-oxidant
Agent and crosslinking agent and needle shape wollastonite powder, improve the mechanical property of thermoplastic polyurethane comprehensively, and heat resistance improves impact
Toughness, improves the surface property of thermoplastic polyurethane, with high antioxygenic property and prevents what light aging and product from fading
Problem；The cost of product can also be greatly lowered, product level is improved.
The composite assistant being used for during thermoplastic polyurethane is modified of the present invention is mainly used in the modification of thermoplastic polyurethane,
The composite assistant is applicable to polyurethane, thermoplastic polyurethane, polyester, makrolon, polystyrene and polyolefin masterbatch etc. and gathered
Compound system, is widely used in the neck such as plastics, rubber, asbestos alternative, paint, automobile, electronics, machinery and Aero-Space
Domain.
Embodiment
Technical scheme and effect are further described with reference to example.
Embodiment one：Prepare composite:By 5 parts of ultra-violet absorber of mass fraction, the antioxygen that 30 parts of mass fraction
Agent, the crosslinking agent that 5 parts of mass fraction, the needle shape wollastonite powder that 60 parts of mass fraction is sufficiently mixed uniform obtain in high mixer
Composite assistant composite assistants in being modified for thermoplastic polyurethane are shown in attached to the improvement situation of thermoplastic polyurethane performance
Table 1.
Embodiment two：Prepare composite:By 5 parts of ultra-violet absorber of mass fraction, the antioxygen that 40 parts of mass fraction
Agent, the crosslinking agent that 5 parts of mass fraction, 50 parts of needle shape wollastonite powders of mass fraction are sufficiently mixed in high mixer uniformly to be obtained
Composite assistant composite assistants in being modified for thermoplastic polyurethane are seen attached list to the improvement situation of thermoplastic polyurethane performance
1。
Embodiment three：Prepare composite:By 5 parts of ultra-violet absorber of mass fraction, the antioxygen that 45 parts of mass fraction
Agent, the crosslinking agent that 5 parts of mass fraction, 55 parts of needle shape wollastonite powders of mass fraction are sufficiently mixed in high mixer uniformly to be obtained
Composite assistant in being modified for thermoplastic polyurethane.Composite assistant sees attached list 1 to the improvement situation of thermoplastic polyurethane performance.
Improvement situation of the composite assistant of subordinate list 1 to thermoplastic polyurethane performance
Claims (6)
1. a kind of composite assistant being modified for thermoplastic polyurethane, is in the composite containing 100 parts of mass fraction,
3-6 parts of ultra-violet absorbers, 30-40 parts of antioxidant, 3-6 parts of crosslinking agents, the 50-60 parts of needle-like silicon Jing Guo coupling agent treatment
Limestone flour.
2. the composite assistant being used for during thermoplastic polyurethane is modified described in claim 1, it is characterised in that ultraviolet containing 3-6 parts
Light absorbers, the ultra-violet absorber is：2- (2'- hydroxyl -3'- tertiary butyl -5'- aminomethyl phenyls) -5- chlorobenzotriazoles or
2- (2- hydroxyl -3,5- di-tert-pentyl-phenyls) BTAs or 2- (double (2,4- the 3,5-dimethylphenyls) -1,3,5- triazines -2- of 4,6-
Base) -5- octyloxies phenol or 2-（4,6- diphenyl -1,3,5-triazines -2）- 5- n-hexane epoxide phenol.
3. the composite assistant being used for during thermoplastic polyurethane is modified described in claim 1, it is characterised in that contain 30-40 parts
Antioxidant, the antioxidant be β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyl) propionic acid or four [β-
（3,5- di-t-butyl 4- hydroxy phenyls）Propionic acid] pentaerythritol ester or N, N '-bis- [β-(3,5- di-tert-butyl-hydroxy phenyls)
Propionyl] hydrazine, three [2.4- di-tert-butyl-phenyls] phosphite esters.
4. the composite assistant being used for during thermoplastic polyurethane is modified described in claim 1, it is characterised in that contain 3-6 parts of crosslinkings
Agent, the crosslinking agent Wei oxazoline classes, are 1,3-, phenyl-bis- (bisoxazolines）Or Isosorbide-5-Nitrae-, phenyl-bis- (bisoxazolines）、
Or double (bisoxazolines）.
5. the composite assistant being used for during thermoplastic polyurethane is modified described in claim 1, it is characterised in that contain 50-60 parts of pins
Shape wollastonite in powder, wherein the needle shape wollastonite powder is the natural acicular wollastonite powder Jing Guo coupling agent treatment, the coupling
Agent is type siloxane or titanate ester.
6. the preparation method of the composite assistant being used for during thermoplastic polyurethane is modified described in claim 1:By 3-6 parts of ultraviolets
Absorbent, 30-40 parts of antioxidant, 3-6 parts of crosslinking agents, 50-60 parts of needle shape wollastonite powders, which are adequately mixed, uniformly to be obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710290868.3A CN106987114A (en) | 2017-04-28 | 2017-04-28 | A kind of preparation for the composite assistant being modified for thermoplastic polyurethane |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710290868.3A CN106987114A (en) | 2017-04-28 | 2017-04-28 | A kind of preparation for the composite assistant being modified for thermoplastic polyurethane |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111019494A (en) * | 2019-12-31 | 2020-04-17 | 南京德嘉玻璃钢材料有限公司 | High-weather-resistance gel coat and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532881A (en) * | 2011-12-30 | 2012-07-04 | 大连亚泰科技新材料有限公司 | Acicular wollastonite powder composite material for nylon 6 modification and preparation method thereof |
-
2017
- 2017-04-28 CN CN201710290868.3A patent/CN106987114A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102532881A (en) * | 2011-12-30 | 2012-07-04 | 大连亚泰科技新材料有限公司 | Acicular wollastonite powder composite material for nylon 6 modification and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 毛晨曦等: "噁唑啉基扩链剂的合成及其应用研究", 《塑料助剂》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111019494A (en) * | 2019-12-31 | 2020-04-17 | 南京德嘉玻璃钢材料有限公司 | High-weather-resistance gel coat and preparation method thereof |
| CN111019494B (en) * | 2019-12-31 | 2021-10-01 | 南京德嘉玻璃钢材料有限公司 | High-weather-resistance gel coat and preparation method thereof |
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