CN108102065B - Fiber-reinforced thermoplastic polyurethane for bulletproof glass and preparation method thereof - Google Patents
Fiber-reinforced thermoplastic polyurethane for bulletproof glass and preparation method thereof Download PDFInfo
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- CN108102065B CN108102065B CN201711099948.7A CN201711099948A CN108102065B CN 108102065 B CN108102065 B CN 108102065B CN 201711099948 A CN201711099948 A CN 201711099948A CN 108102065 B CN108102065 B CN 108102065B
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- C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
- C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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- B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
- B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
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- B32B27/00—Layered products comprising a layer of synthetic resin
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- C08G18/40—High-molecular-weight compounds
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- 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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- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
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- C08G18/72—Polyisocyanates or polyisothiocyanates
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- C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
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- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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- C09J175/08—Polyurethanes from polyethers
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Abstract
The invention discloses fiber reinforced thermoplastic polyurethane for bulletproof glass, which comprises the following raw material components in parts by weight: 20-35 parts of aliphatic diisocyanate, 50-55 parts of polytetrahydrofuran ethylene oxide copolyether with the average molecular weight of 2000-4000, 6-12 parts of 1, 4-butanediol, 5-15 parts of glass fiber modified by gamma-aminopropyltriethoxysilane, and dibutyltin dilaurate accounting for 0.03-0.08% of the total weight of other raw material components. The obtained fiber-reinforced thermoplastic polyurethane has excellent adhesion to glass plates and polycarbonate plates, high transparency, high yellowing resistance and aging resistance, and excellent tensile strength, fracture toughness and impact strength, can obviously improve various service performances of the bulletproof glass, and promotes the application development of the bulletproof glass. The preparation of the thermoplastic polyurethane material of the invention obtains the sandwich material more suitable for the bulletproof glass by limiting the mixing and adding sequence of different raw material components.
Description
Technical Field
The invention relates to the technical field of thermoplastic polyurethane materials, in particular to fiber reinforced thermoplastic polyurethane for bulletproof glass, and also relates to a preparation method and application of the material.
Background
The bulletproof glass has the appearance of common glass and the behavior of transmitting light, absorbs partial energy and shock wave pressure generated in the process of impact and explosion by a multilayer composite structure, has good impact resistance, penetration resistance and safety, has the functions of theft prevention, bullet prevention and explosion prevention, and can be widely applied to the fields of aviation, vehicles, ships, security and the like. The traditional bulletproof glass is manufactured by bonding a plurality of layers of glass by adopting a transparent bonding material, and the bulletproof capability is improved by depending on the thickness of the glass, the number of interlayer layers and the performance of the bonding material. The bullet-proof glass composed of multiple layers of glass is too thick and heavy due to the high density of the glass material, which brings inconvenience to installation and use.
In the novel bulletproof glass structure, the polycarbonate plate is used for replacing the last layer of glass plate, so that the impact resistance of the bulletproof glass can be obviously improved under the same weight and thickness, and the performance of the bulletproof glass in the structure is particularly important to the impact resistance and the service performance as a transparent gluing material of an interlayer material. Films made of polyvinyl butyral (PVB) are currently used as interlayers in bulletproof glass, and PVB film has a fatal disadvantage of poor flexibility at low temperature, and significantly increased brittleness when the ambient temperature is lower than 0 ℃, that is, the bonding strength of the PVB film to glass and polycarbonate plates is reduced along with the reduction of temperature. This has resulted in ballistic glass made using PVB film not being usable at low temperatures.
Thermoplastic Polyurethane (TPU) has excellent low temperature resistance, high tensile strength and excellent adhesion with polycarbonate, and is one of potential materials for replacing PVB films to be applied to bulletproof glass. The bulletproof glass has special requirements on optical performance besides strength, and no TPU material with excellent performance and suitable for bulletproof glass exists at present.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides fiber reinforced thermoplastic polyurethane for bulletproof glass, and the thermoplastic polyurethane material has high transparency, high yellowing resistance, high adhesion and high impact resistance and is suitable for the special performance requirements of bulletproof glass.
In order to achieve the aim, the invention provides fiber reinforced thermoplastic polyurethane for bulletproof glass, which comprises the following raw material components in parts by weight:
20-35 parts of aliphatic diisocyanate;
50-55 parts of polytetrahydrofuran ethylene oxide copolyether with the average molecular weight of 2000-4000;
6-12 parts of 1, 4-butanediol;
5-15 parts of gamma-aminopropyltriethoxysilane-modified glass fiber;
and dibutyltin dilaurate accounting for 0.03-0.08% of the total weight of other raw material components.
As an interlayer material of the bulletproof glass, the bulletproof glass needs to have excellent adhesion with a glass plate and a polycarbonate plate to ensure the stable structure of the bulletproof glass, also needs to have good transparency, yellowing resistance and aging resistance, provides basic service performance and service life of the bulletproof glass, and more importantly needs to have excellent tensile and impact resistance, so that the bulletproof glass is endowed with more effective bulletproof capability. According to the invention, polytetrahydrofuran ethylene oxide copolyether and aliphatic diisocyanate which do not contain aromatic functional groups are taken as raw materials, 1, 4-butanediol is taken as a chain extender, dibutyltin dilaurate is taken as a catalyst, and gamma-aminopropyltriethoxysilane modified glass fibers are particularly added to prepare a thermoplastic polyurethane material, after condensation and crosslinking reaction of the raw materials, the TPU material which can excellently bond a glass plate and a polycarbonate plate, has high transparency, high yellowing resistance and ageing resistance is obtained, and belongs to a fiber-reinforced type, the tensile strength, fracture toughness and impact strength of the TPU material are extremely excellent, and the use performance of the bulletproof glass can be obviously improved when the TPU material is used as a sandwich material of the bulletproof glass, so that the application development of the bulletproof glass is promoted.
As a limitation to the above technical means, the aliphatic diisocyanate is at least one of Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane-4, 4' -diisocyanate (HMDI), and 1, 3-bis (isocyanatomethyl) cyclohexane.
As a limitation to the technical scheme, the functionality of the polytetrahydrofuran ethylene oxide copolyether is 2.0-2.3.
As a limitation to the technical scheme, the molecular weight of the polytetrahydrofuran ethylene oxide copolyether is 3100, and the hydroxyl value is 40.12mg KOH/g.
As the limitation to the technical scheme, the glass fiber is chopped glass fiber, and the fiber length is 2-6 mm.
As a limitation to the above technical means, the chopped glass fibers have a fiber length of 3 mm.
Further limiting the material selection of raw materials of aliphatic diisocyanate, polytetrahydrofuran ethylene oxide copolyether and glass fiber, so as to be beneficial to the performance optimization of the thermoplastic polyurethane material.
Meanwhile, the invention also provides a preparation method of the fiber reinforced thermoplastic polyurethane for the bulletproof glass, which comprises the following steps:
a. obtaining glass fiber modified by gamma-aminopropyltriethoxysilane;
b. mixing glass fiber modified by gamma-aminopropyltriethoxysilane and 1, 4-butanediol to obtain a material A, mixing dibutyltin dilaurate and polytetrahydrofuran ethylene oxide copolyether to obtain a material B, taking aliphatic diisocyanate as a material C, simultaneously injecting the three materials into a double-screw continuous reaction extruder by controlling the proportion of the materials A, B and C, reacting at the temperature of 160-260 ℃ and the die head pressure of 2MPa, and granulating and drying an extruded product after the reaction to obtain a particle product of the fiber-reinforced thermoplastic polyurethane.
According to the preparation process of the thermoplastic polyurethane material, the mixing and adding sequence of different raw materials is limited, modified glass fibers are mixed with a chain extender, then the flow of the materials is controlled and the materials are added into a double-screw extruder together according to the raw material proportion, the chain extender is used for guiding the raw materials of polytetrahydrofuran ethylene oxide copolyether and aliphatic diisocyanate to carry out polymerization and crosslinking reaction at a specific reaction temperature and under a specific pressure, the modified glass fibers are uniformly constructed in a thermoplastic polyurethane molecular chain under the promoting and auxiliary dispersing effects of the chain extender in the reaction, and the fiber-reinforced thermoplastic polyurethane material is obtained.
As a limitation to the above technical solution, the glass fiber modified by γ -aminopropyltriethoxysilane is prepared by the following method:
adding the glass fiber into an ethanol solution of gamma-aminopropyltriethoxysilane, carrying out ultrasonic oscillation treatment at room temperature, then taking out and drying to obtain the gamma-aminopropyltriethoxysilane modified glass fiber; the ultrasonic oscillation treatment mode is that ultrasonic oscillation is continuously carried out for 90 times at room temperature and ultrasonic power of 600W, wherein each ultrasonic oscillation lasts for 60s and is separated by 20 s.
As a limitation to the technical scheme, the dosage of the gamma-aminopropyl triethoxysilane is 15% of the weight of the glass fiber, and the volume concentration of the ethanol solution of the gamma-aminopropyl triethoxysilane is 20%.
The method adopts gamma-aminopropyltriethoxysilane as a modifier to modify common glass fibers through specific ultrasonic oscillation treatment, and further limits the use amount and use concentration of the modifier to obtain modified glass fibers with more applicable performance, thereby facilitating the crosslinking reaction of the modified glass fibers and raw materials and promoting the preparation of later-stage fiber-reinforced thermoplastic polyurethane materials.
Meanwhile, the invention also provides the application of the fiber reinforced thermoplastic polyurethane for the bulletproof glass, namely the fiber reinforced thermoplastic polyurethane is used for bonding the glass layer and the polycarbonate layer in the manufacturing of the bulletproof glass.
In conclusion, the fiber-reinforced thermoplastic polyurethane for bulletproof glass, which is obtained by adopting the technical scheme of the invention, is prepared by taking polytetrahydrofuran ethylene oxide copolyether and aliphatic diisocyanate which do not contain aromatic functional groups as raw materials, 1, 4-butanediol as a chain extender, dibutyltin dilaurate as a catalyst and specially adding glass fibers modified by gamma-aminopropyltriethoxysilane through condensation and crosslinking reaction, and can be used as a sandwich material of bulletproof glass, so that the fiber-reinforced thermoplastic polyurethane not only can excellently bond a glass plate and a polycarbonate plate, but also has high transparency, high yellowing resistance and aging resistance, and has extremely excellent tensile strength, fracture toughness and impact strength, can obviously improve various service performances of bulletproof glass, and promotes the application development of high-performance bulletproof glass. The thermoplastic polyurethane material disclosed by the invention is simple in preparation process, and the modified glass fiber and the chain extender are firstly mixed and then uniformly built in a thermoplastic polyurethane molecular chain by limiting the mixing and adding sequence of different raw materials, so that the sandwich material more suitable for the bulletproof glass is obtained.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the 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.
Example one
This example relates to fiber reinforced thermoplastic polyurethanes for use in ballistic glass and their preparation.
The fiber reinforced thermoplastic polyurethane for the bulletproof glass comprises the following raw material components in parts by weight:
20-35 parts of aliphatic diisocyanate;
50-55 parts of polytetrahydrofuran ethylene oxide copolyether with the average molecular weight of 2000-4000;
6-12 parts of 1, 4-butanediol;
5-15 parts of gamma-aminopropyltriethoxysilane-modified glass fiber;
and dibutyltin dilaurate accounting for 0.03-0.08% of the total weight of other raw material components.
The preparation method comprises the following steps:
a. obtaining glass fiber modified by gamma-aminopropyltriethoxysilane;
b. mixing glass fiber modified by gamma-aminopropyltriethoxysilane and 1, 4-butanediol to obtain a material A, mixing dibutyltin dilaurate and polytetrahydrofuran ethylene oxide copolyether to obtain a material B, using aliphatic diisocyanate as a material C, controlling the proportion of the material A, the material B and the material C, simultaneously injecting the three materials into a double-screw continuous reaction extruder, reacting at the temperature of 160-260 ℃ and the die head pressure of 2MPa, extruding a product after the reaction is complete, and granulating and drying to obtain a particle product of the fiber-reinforced thermoplastic polyurethane.
The fiber-reinforced thermoplastic polyurethanes of the different examples were prepared as described above, the materials and amounts of the examples being shown in the following table:
example two
This example relates to the properties of the fiber-reinforced thermoplastic polyurethane material obtained in example one, as shown in the following table, wherein the haze and YI of the test pieces were measured by x-rite Ci 7600 series spectrometer, and other properties were measured according to the national standard requirements.
The above table shows that the fiber-reinforced thermoplastic polyurethane of the present invention is significantly superior to a common PVB film in tensile strength, optical performance and low temperature resistance, and can be used for bullet-proof glass instead of a PVB film, and the service performance of the bullet-proof glass can be significantly improved.
In conclusion, the fiber-reinforced thermoplastic polyurethane can be used for excellently bonding a glass plate and a polycarbonate plate, has high transparency, high yellowing resistance and aging resistance, and has extremely excellent tensile strength, fracture toughness and impact strength, so that various service performances of the bulletproof glass can be remarkably improved, and the application development of the bulletproof glass is promoted. The thermoplastic polyurethane material disclosed by the invention is simple in preparation process, and the modified glass fiber and the chain extender are firstly mixed and then uniformly built in a thermoplastic polyurethane molecular chain by limiting the mixing and adding sequence of different raw materials, so that the sandwich material more suitable for the bulletproof glass is obtained.
Claims (8)
1. The fiber-reinforced thermoplastic polyurethane for the bulletproof glass is characterized by comprising the following raw material components in parts by weight:
20-35 parts of aliphatic diisocyanate;
57.91 parts, 56.71 parts or 57.59 parts of polytetrahydrofuran ethylene oxide copolyether, with the molecular weight of 3100 and the hydroxyl value of 40.12mg KOH/g;
6-12 parts of 1, 4-butanediol;
5-15 parts of gamma-aminopropyltriethoxysilane-modified glass fiber;
and dibutyltin dilaurate accounting for 0.03-0.08% of the total weight of other raw material components;
the aliphatic diisocyanate is at least one of hexamethylene diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate and 1, 3-di (isocyanotomethyl) cyclohexane.
2. The fiber-reinforced thermoplastic polyurethane for ballistic glass according to claim 1, characterized in that: the functionality of the polytetrahydrofuran ethylene oxide copolyether is 2.0-2.3.
3. The fiber-reinforced thermoplastic polyurethane for ballistic glass according to claim 1, characterized in that: the glass fiber is chopped glass fiber, and the fiber length is 2-6 mm.
4. The fiber-reinforced thermoplastic polyurethane for ballistic glass according to claim 3, characterized in that: the chopped glass fibers have a fiber length of 3 mm.
5. A process for the preparation of the fiber-reinforced thermoplastic polyurethane for ballistic glass according to any one of claims 1 to 4, comprising the steps of:
a. obtaining glass fiber modified by gamma-aminopropyltriethoxysilane;
b. mixing glass fiber modified by gamma-aminopropyltriethoxysilane and 1, 4-butanediol to obtain a material A, mixing dibutyltin dilaurate and polytetrahydrofuran ethylene oxide copolyether to obtain a material B, taking aliphatic diisocyanate as a material C, simultaneously injecting the three materials into a double-screw continuous reaction extruder by controlling the proportion of the materials A, B and C, reacting at the temperature of 160-260 ℃ and the die head pressure of 2MPa, and granulating and drying an extruded product after the reaction to obtain a particle product of the fiber-reinforced thermoplastic polyurethane.
6. The process for the preparation of fiber-reinforced thermoplastic polyurethane for ballistic glass according to claim 5, characterized in that the glass fibers modified with γ -aminopropyltriethoxysilane are prepared by the following process:
adding the glass fiber into an ethanol solution of gamma-aminopropyltriethoxysilane, carrying out ultrasonic oscillation treatment at room temperature, then taking out and drying to obtain the gamma-aminopropyltriethoxysilane modified glass fiber; the ultrasonic oscillation treatment mode is that ultrasonic oscillation is continuously carried out for 90 times at room temperature and ultrasonic power of 600W, wherein each ultrasonic oscillation lasts for 60s and is separated by 20 s.
7. The process for the preparation of fiber-reinforced thermoplastic polyurethane for ballistic glass according to claim 6, characterized in that: the dosage of the gamma-aminopropyl triethoxysilane is 15% of the weight of the glass fiber, and the volume concentration of the ethanol solution of the gamma-aminopropyl triethoxysilane is 20%.
8. Use of the fiber-reinforced thermoplastic polyurethane according to any of claims 1 to 4 for ballistic glass, characterized in that: the fiber-reinforced thermoplastic polyurethane is used for bonding a glass layer and a polycarbonate layer in the process of manufacturing the bulletproof glass.
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| CN109233256A (en) * | 2018-09-30 | 2019-01-18 | 山东诺威聚氨酯股份有限公司 | Fiberglass reinforced is used for the TPU material and preparation method thereof of automobile anti-collision rod |
| CN109593350A (en) * | 2018-12-06 | 2019-04-09 | 长沙盾甲新材料科技有限公司 | For shellproof polyurethane-fibrous composite and preparation method thereof |
| CN111961186A (en) * | 2020-08-27 | 2020-11-20 | 栖霞市兴邦新材料科技有限公司 | Thermoplastic polyurethane elastomer and preparation method thereof |
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