Composite material of non-isocyanate polyurethane resin for pultrusion and preparation method thereof

Abstract

The invention relates to the technical field of composite materials, in particular to a non-isocyanate polyurethane resin composite material for pultrusion and a preparation method of the non-isocyanate polyurethane resin composite material for pultrusion. Green and sustainable raw materials and a green and environment-friendly process route are used, and the composite material of the non-isocyanate polyurethane resin for pultrusion, which is prepared by taking the non-isocyanate polyurethane as the raw material, can be used for manufacturing solar brackets, telegraph poles, door and window frames and cable brackets; in this way, the technical problems that in the prior art, polyurethane is prepared from isocyanate and polyol as raw materials, and the used isocyanate is active in chemical property, large in toxicity, poor in water resistance, inconvenient to store and transport and environment-friendly are solved.

Description

Technical Field

[0001] The invention relates to the technical field of composite materials, and in particular to a composite material of non-isocyanate polyurethane resin for pultrusion and a preparation method thereof. Background Art

[0002] The pultrusion process is a molding process that forms and solidifies impregnated continuous fibers through an extrusion die under the action of traction, and continuously and massively produces various linear profiles with constant cross-sectional dimensions. The pultrusion process has high production efficiency, high strength and stiffness-to-weight ratio, and strong designability. Traditional resins used in the pultrusion process include polyester, unsaturated resin, phenolic resin, epoxy resin, etc. Polyurethane resin stands out from traditional resins with its excellent mechanical properties, low-pressure molding, fast curing, and no styrene volatilization, and has become the "new favorite" in the resin-based composite material industry.

[0003] Traditional polyurethane is prepared with isocyanate and polyol as raw materials. The isocyanate used is chemically active, highly toxic and has poor water resistance, which leads to problems of inconvenience in storage and transportation and environmental pollution. Summary of the invention

[0004] The object of the present invention is to provide a composite material of a non-isocyanate polyurethane resin for pultrusion and a preparation method thereof, aiming to solve the technical problems in the prior art that polyurethane is prepared from isocyanate and polyol as raw materials, the isocyanate used has active chemical properties, high toxicity and poor water resistance, and there are problems of inconvenience in storage and transportation and environmental pollution.

[0005] To achieve the above purpose, the present invention adopts a composite material of non-isocyanate polyurethane resin for pultrusion, which includes 75-85% of continuous fibers and 15-25% of non-isocyanate polyurethane resin, wherein the non-isocyanate polyurethane resin includes 20-40 parts of polyamine, 50-80 parts of polycyclic carbonate, 0.1-0.5 parts of catalyst, 0-0.5 parts of antioxidant, 0-0.5 parts of ultraviolet absorber, 0-0.5 parts of defoamer and 0-1 parts of release agent.

[0006] Wherein, the polyamine is one or more combinations of ethylenediamine, diethylenetriamine, isophoronediamine, and aminosiloxane oligomer.

[0007] Wherein, the catalyst is one or more combinations of tin catalysts, zinc catalysts or bismuth catalysts.

[0008] Wherein, the antioxidant is one or more combinations of hindered phenols and secondary aromatic amines.

[0009] Wherein, the ultraviolet absorber is benzotriazole.

[0010] Wherein, the defoaming agent is a fluorine defoaming agent.

[0011] Wherein, the release agent is one or more combinations of polyether silicone oil, stearic acid and paraffin powder.

[0012] The continuous fibers include one or more combinations of glass fibers, carbon fibers, natural fibers, aramid fibers, basalt fibers, polypropylene, and nylon.

[0013] Wherein, the polycyclic carbonate main component is the following structure:

[0014]

[0015] R1 and R2 are one of substituted or unsubstituted C1-C20 straight chain or branched alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C3-C20 heterocycloalkyl groups, and substituted or unsubstituted C6-C20 aryl groups.

[0016] The present invention also provides a method for preparing a composite material of a non-isocyanate polyurethane resin for pultrusion, which is used to prepare the composite material of the non-isocyanate polyurethane resin for pultrusion as described above.

[0017] The steps include:

[0018] Step 1: Weigh the polyamine in proportion and place it in the barrel of the glue injection machine A;

[0019] Step 2: weigh polycyclic carbonate, catalyst, antioxidant, ultraviolet absorber, defoamer and release agent in proportion, stir and mix them evenly at a low speed, and then place them in the barrel of the glue injection machine B;

[0020] Step 3: Mix the components in barrel A and barrel B in a ratio of 1.5:1 through a glue injection machine, inject into a glue injection box to obtain non-isocyanate polyurethane and inject into a mold. The mold temperature is controlled in two stages, with the head at 100-120°C and the rear end at 160-180°C.

[0021] Step 4: Pass the continuous fiber through the die head and impregnate the continuous fiber with non-isocyanate polyurethane;

[0022] Step 5, pultruding the continuous fiber impregnated with the mixed resin through the middle section of the mold to obtain a composite material;

[0023] Step 6: When the composite material passes through the tail of the mold, it is cooled to 70-90°C by air cooling.

[0024] The present invention discloses a composite material of a non-isocyanate polyurethane resin for pultrusion and a preparation method thereof. First, a polyamine is weighed in proportion and placed in a barrel A of a glue injection machine; then, a polycyclic carbonate, a catalyst, an antioxidant, an ultraviolet absorber, a defoamer and a release agent are weighed in proportion, stirred and mixed evenly at a low speed, and then placed in a barrel B of a glue injection machine; then, the components in barrel A and the components in barrel B are mixed in a ratio of 1.5:1 through a glue injection machine and injected into a glue injection box to obtain a non-isocyanate polyurethane and driven into a mold, and the mold temperature is controlled in two stages, with the head being 100-120°C and the rear end being 160-180°C; then, a continuous fiber is passed through the head of the mold to be impregnated with the non-isocyanate polyurethane; then, the continuous fiber impregnated with the mixed resin is pulled through the middle section of the mold. The composite material is extruded and then cooled to 70-90°C by air cooling when the composite material passes through the tail of the die. The non-isocyanate polyurethane (NIPU) prepared by the present invention has good hydrolysis stability, chemical resistance, mechanical resistance and heat resistance, and uses green and sustainable raw materials and green environmentally friendly process routes. The composite material of non-isocyanate polyurethane resin for pultrusion prepared by using non-isocyanate polyurethane as raw material can be used to manufacture solar brackets, electric poles, door and window frames and cable brackets. In this way, the technical problems that polyurethane is prepared from isocyanate and polyol as raw materials in the prior art, the isocyanate used is chemically active, has high toxicity and poor water resistance, and has the problems of inconvenience in storage and transportation and environmental pollution are solved. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0026] Figure 1 It is a preparation flow chart of the polycyclic carbonate of the present invention. DETAILED DESCRIPTION

[0027] Embodiments of the present invention are described in detail below. Examples of the embodiments are shown in the accompanying drawings. The embodiments described below with reference to the accompanying drawings are exemplary and are intended to be used to explain the present invention, but should not be construed as limiting the present invention.

[0028] The invention provides a composite material of non-isocyanate polyurethane resin for pultrusion, comprising 75-85% of continuous fibers and 15-25% of non-isocyanate polyurethane resin, wherein the non-isocyanate polyurethane resin comprises 20-40 parts of polyamine, 50-80 parts of polycyclic carbonate, 0.1-0.5 parts of catalyst, 0-0.5 parts of antioxidant, 0-0.5 parts of ultraviolet absorber, 0-0.5 parts of defoamer and 0-1 parts of release agent.

[0029] The polyamine is one or more combinations of ethylenediamine, diethylenetriamine, isophoronediamine and aminosiloxane oligomer.

[0030] The catalyst is one or more combinations of tin catalysts, zinc catalysts or bismuth catalysts.

[0031] The antioxidant is one or more combinations of hindered phenols and secondary aromatic amines.

[0032] The ultraviolet absorber is benzotriazole.

[0033] The defoaming agent is a fluorine defoaming agent.

[0034] The release agent is one or more combinations of polyether silicone oil, stearic acid and paraffin powder.

[0035] The continuous fibers include one or more combinations of glass fibers, carbon fibers, natural fibers, aramid fibers, basalt fibers, polypropylene, and nylon.

[0036] The polycyclic carbonate main component is the following structure:

[0037]

[0038] R1 and R2 are one of substituted or unsubstituted C1-C20 straight chain or branched alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C3-C20 heterocycloalkyl groups, and substituted or unsubstituted C6-C20 aryl groups.

[0039] See also Figure 1 , Figure 1 The present invention also provides a method for preparing a composite material of a non-isocyanate polyurethane resin for pultrusion, which is used to prepare the composite material of the non-isocyanate polyurethane resin for pultrusion as described above.

[0040] The steps include:

[0041] Step 1: Weigh the polyamine in proportion and place it in the barrel of the glue injection machine A;

[0042] Step 2: weigh polycyclic carbonate, catalyst, antioxidant, ultraviolet absorber, defoamer and release agent in proportion, stir and mix them evenly at a low speed, and then place them in the barrel of the glue injection machine B;

[0043] Step 3: Mix the components in barrel A and barrel B in a ratio of 1.5:1 through a glue injection machine, inject into a glue injection box to obtain non-isocyanate polyurethane and inject into a mold. The mold temperature is controlled in two stages, with the head at 100-120°C and the rear end at 160-180°C.

[0044] Step 4: Pass the continuous fiber through the die head and impregnate the continuous fiber with non-isocyanate polyurethane;

[0045] Step 5, pultruding the continuous fiber impregnated with the mixed resin through the middle section of the mold to obtain a composite material;

[0046] Step 6: When the composite material passes through the tail of the mold, it is cooled to 70-90°C by air cooling.

[0047] The polycyclic carbonate is prepared as follows:

[0048] Trimethylolpropane-2-hydroxyethyl isocyanurate (THEIC), dehydrated castor oil fatty acid (DCOFA) and a catalyst were placed in a three-necked flask and stirred continuously at about 170° C. for 6 h under a N2 atmosphere to obtain an intermediate product 1 (TEFA).

[0049] TEFA, acetic acid and catalyst were placed in a three-necked flask and stirred continuously at 1500 rpm for 30 minutes. Hydrogen peroxide was added and reacted at 60°C for 6 hours in a N2 atmosphere. After the mixture was cooled, it was separated with a separatory funnel, neutralized, dried and washed to obtain intermediate product 2 (ETEFA).

[0050] ETTFA and tetrabutylammonium bromide (TBAB) were placed in a reactor and reacted at 110°C for 6 hours in a 2MPa CO2 atmosphere. After the reactor was cooled, the pressure in the reactor was slowly released to obtain a crude product. The crude product was washed and dried to obtain cyclocarbonate fatty acid (CTEFA).

[0051] Embodiment 1:

[0052] Take 22 parts of isophorone diamine in proportion and put them in the barrel of glue injection machine A, take 74.5 parts of CTEFA, 0.2 parts of catalyst, 0.3 parts of antioxidant, 0.5 parts of UV absorber, 0.5 parts of defoamer and 2 parts of release agent in proportion and put them in the barrel of glue injection machine B;

[0053] The components in barrel A and barrel B are mixed and injected into a glue injection box at a weight ratio of 1.5:1 through a glue injection machine to obtain a non-isocyanate polyurethane resin, 78% of continuous fibers are impregnated with 22% of the non-isocyanate polyurethane resin, and the fibers are pultruded to obtain a composite material of non-isocyanate polyurethane resin for pultrusion.

[0054] The process parameters of the pultrusion molding are: the temperature of the first zone is 100-120°C, the temperature of the second zone is 160-180°C, and the pultrusion speed is 0.6-1m / min. Cooling and demoulding. According to the national standards GB / T 1447-2005 and GB / T1449-2005, the tensile strength, bending strength and bending modulus of the prepared composite material are tested. The tensile strength sample size is 200mm (length) × 10mm (width), and the bending strength sample size is 80mm (length) × 10mm (width). The tensile strength of the composite material is measured to be 961MPa, the bending strength is 937MPa, and the bending elastic modulus is 30GPa.

[0055] Embodiment 2:

[0056] In this embodiment, the polycyclic carbonate is the cyclic carbonate (CTEFA) in Example 1, the polyamine is 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane (Suzhou Qihang Biotechnology Co., Ltd.), and the remaining steps are consistent with Example 1.

[0057] The experimental steps were consistent with those in Example 1. The composite material had a tensile strength of 1121 MPa, a flexural strength of 1281 MPa, and a flexural modulus of 35 GPa.

[0058] A composite material of a non-isocyanate polyurethane resin for pultrusion and a preparation method thereof according to the present embodiment are used. First, a polyamine is weighed in proportion and placed in a barrel A of a glue injection machine; then, a polycyclic carbonate, a catalyst, an antioxidant, an ultraviolet absorber, a defoamer and a release agent are weighed in proportion and mixed evenly at a low speed, and then placed in a barrel B of a glue injection machine; then, the components in barrel A and the components in barrel B are mixed in a ratio of 1.5:1 through a glue injection machine and injected into a glue injection box to obtain a non-isocyanate polyurethane and injected into a mold. The mold temperature is controlled in two stages, with the head at 100-120°C and the rear end at 160-180°C; then, a continuous fiber is passed through the head of the mold to be impregnated with the non-isocyanate polyurethane; then, the continuous fiber impregnated with the mixed resin is passed through the middle of the mold. The composite material is pultruded by a plurality of sections to obtain a composite material; finally, when the composite material passes through the tail of the die, it is cooled to 70-90° C. by air cooling. The non-isocyanate polyurethane (NIPU) prepared by the present invention has good hydrolysis stability, chemical resistance, mechanical resistance and heat resistance, and uses green and sustainable raw materials and a green and environmentally friendly process route. The composite material of the non-isocyanate polyurethane resin for pultrusion prepared by using the non-isocyanate polyurethane as a raw material can be used to manufacture solar brackets, electric poles, door and window frames and cable brackets. In this way, the technical problems that the polyurethane is prepared from isocyanate and polyol as raw materials in the prior art, the isocyanate used is chemically active, has high toxicity and poor water resistance, and has the problems of inconvenience in storage and transportation and environmental pollution are solved.

[0059] What is disclosed above is only a preferred embodiment of the present invention, and it certainly cannot be used to limit the scope of rights of the present invention. Ordinary technicians in this field can understand that all or part of the processes of the above embodiment and equivalent changes made according to the claims of the present invention still fall within the scope of the invention.

Claims

1. A composite material of a non-isocyanate polyurethane resin for pultrusion, characterized in that: The invention comprises 75-85% of continuous fibers and 15-25% of non-isocyanate polyurethane resin, wherein the non-isocyanate polyurethane resin comprises 20-40 parts of polyamine, 50-80 parts of polycyclic carbonate, 0.1-0.5 parts of catalyst, 0-0.5 parts of antioxidant, 0-0.5 parts of ultraviolet absorber, 0-0.5 parts of defoamer and 0-1 parts of release agent.

2. The composite material of non-isocyanate polyurethane resin for pultrusion according to claim 1, characterized in that: The polyamine is one or more combinations of ethylenediamine, diethylenetriamine, isophoronediamine and aminosiloxane oligomer.

3. The composite material of non-isocyanate polyurethane resin for pultrusion and the preparation method thereof according to claim 2, characterized in that: The catalyst is one or more combinations of tin catalysts, zinc catalysts or bismuth catalysts.

4. The composite material of non-isocyanate polyurethane resin for pultrusion according to claim 3, characterized in that: The antioxidant is one or more combinations of hindered phenols and secondary aromatic amines.

5. The composite material of non-isocyanate polyurethane resin for pultrusion according to claim 4, characterized in that: The ultraviolet absorber is benzotriazole.

6. The composite material of non-isocyanate polyurethane resin for pultrusion according to claim 5, characterized in that: The defoaming agent is a fluorine defoaming agent.

7. The composite material of non-isocyanate polyurethane resin for pultrusion according to claim 6, characterized in that: The release agent is one or more combinations of polyether silicone oil, stearic acid and paraffin powder.

8. The composite material of non-isocyanate polyurethane resin for pultrusion according to claim 7, characterized in that: The continuous fibers include one or more combinations of glass fibers, carbon fibers, natural fibers, aramid fibers, basalt fibers, polypropylene, and nylon.

9. The composite material of non-isocyanate polyurethane resin for pultrusion according to claim 8, characterized in that: The polycyclic carbonate main component is the following structure: R1 and R2 are one of substituted or unsubstituted C1-C20 straight chain or branched alkyl groups, substituted or unsubstituted C3-C20 cycloalkyl groups, substituted or unsubstituted C3-C20 heterocycloalkyl groups, and substituted or unsubstituted C6-C20 aryl groups.

10. A method for preparing a composite material of a non-isocyanate polyurethane resin for pultrusion, for preparing the composite material of a non-isocyanate polyurethane resin for pultrusion as claimed in claim 9, characterized in that: The steps include: Step 1: Weigh the polyamine in proportion and place it in the barrel of the glue injection machine A; Step 2: weigh polycyclic carbonate, catalyst, antioxidant, ultraviolet absorber, defoamer and release agent in proportion, stir and mix them evenly at a low speed, and then place them in the barrel of the glue injection machine B; Step 3: Mix the components in barrel A and barrel B in a ratio of 1.5:1 through a glue injection machine, inject into a glue injection box to obtain non-isocyanate polyurethane and inject into a mold. The mold temperature is controlled in two stages, with the head at 100-120°C and the rear end at 160-180°C. Step 4: Pass the continuous fiber through the die head and impregnate the continuous fiber with non-isocyanate polyurethane; Step 5, pultruding the continuous fiber impregnated with the mixed resin through the middle section of the mold to obtain a composite material; Step 6: When the composite material passes through the tail of the mold, it is cooled to 70-90°C by air cooling.

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