Glass microsphere modified polyurethane rigid foam composite profile and preparation method thereof

Abstract

The present application relates to the technical field of thermosetting composite materials, and particularly relates to a glass microsphere modified polyurethane rigid foam composite profile, which comprises alkali-free continuous glass fibers, alkali-free continuous glass fiber mats, thermosetting polyurethane rigid foam materials and glass microspheres, the alkali-free continuous glass fibers are fixed in the profile by the thermosetting polyurethane rigid foam materials, the glass microspheres are coated in the pores of the thermosetting polyurethane rigid foam materials, and the alkali-free continuous glass fiber mats are uniformly embedded in the profile, the alkali-free continuous glass fibers improve the tensile strength of the plate, the alkali-free continuous glass fiber mats improve the shear resistance of the material, the hollow glass microspheres are mixed into the polyurethane foam holes for filling, and since the bulk density of the hollow glass microspheres is less than the free bubble density, the overall weight of the polyurethane rigid foam mixed with the glass microspheres is lighter under the condition of the same compression resistance, and the composite profile provided by the technical scheme has the characteristics of low profile density and high compression resistance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of thermosetting composite materials, in particular to a glass microsphere modified polyurethane rigid foam composite profile and a preparation method thereof. BACKGROUND

[0002] Thermosetting polyurethane is the focus of research in the field of composite materials in recent years, due to its lightweight, high strength, corrosion resistance, good thermal insulation, and strong processability, its application field is increasingly wide. As a branch of thermosetting polyurethane material, polyurethane rigid foam is usually used as a thermal insulation material in the industry.

[0003] With the deepening of research, it is found that the polyurethane rigid foam and the continuous fiber composite can obtain a lightweight and high-strength material, and thus a polyurethane glass fiber composite wood-like product is born. At present, the products mainly include FFU composite material sleeper developed by Japan and HFFP composite material bridge sleeper developed by China Railway Science Research Institute. However, it is found from the actual application that the FFU composite material sleeper is light in weight, labor-saving in processing and installation, but is usually applied to low-load subway and light rail lines, and cannot be applied to heavy-load railways. The HFFP composite material bridge sleeper is heavy in weight, high in load and strong in bearing, which solves the problems of wood sleeper replacement and short maintenance period, but the heavy weight also leads to laborious handling and installation. In view of the above technical problems, the present application provides a glass microsphere modified polyurethane rigid foam composite profile, so as to make the polyurethane rigid foam and the continuous fiber composite material light in weight and high in load. SUMMARY

[0004] The purpose of the present application is to provide a glass microsphere modified polyurethane rigid foam composite profile and a preparation method thereof, so as to make the polyurethane rigid foam glass fiber composite material product light in weight and high in load.

[0005] To achieve the above-mentioned purpose, the present application adopts the following technical scheme:

[0006] The present application provides a glass microsphere modified polyurethane rigid foam composite profile, which comprises alkali-free continuous glass fiber, alkali-free continuous glass fiber felt, thermosetting polyurethane rigid foam material and glass microspheres. The alkali-free continuous glass fiber is fixed in the profile by the thermosetting polyurethane rigid foam material, the glass microspheres are covered in the pores of the thermosetting polyurethane rigid foam material, and the alkali-free continuous glass fiber felt is uniformly embedded in the profile.

[0007] The alkali-free continuous glass fiber is used as a "reinforcing rib" of the formed plate material to improve the tensile strength of the plate material. The alkali-free continuous glass fiber has a linear density of 2400 tex, 4800 tex, 9600 tex, 19200 tex or a mixture of one or more thereof, and has a certain traction tension before being mixed with the thermosetting polyurethane rigid foam material.

[0008] The alkali-free continuous glass fiber mat is used as a shear-resistant layer of the formed plate material to improve the shear resistance of the material. The alkali-free continuous glass fiber mat has a surface density of 300-450 g / m 2 .

[0009] Preferably, the alkali-free continuous glass fiber mat is uniformly distributed in the composite profile in the pressure-bearing direction of the profile.

[0010] Further, the interlayer structure formed by the alkali-free continuous glass fiber mat is not less than 2 layers and not more than 6 layers.

[0011] Further, the upper and lower surfaces of the profile each have at least one layer of the alkali-free continuous glass fiber mat.

[0012] The thermosetting polyurethane rigid foam material is used as a formed material to bond a plurality of alkali-free continuous glass fibers. The thermosetting polyurethane rigid foam resin is a two-component polyurethane resin, specifically a modified isocyanate and a combined polyether polyol.

[0013] The combined polyether polyol is formed by mixing two polyether polyols, a flame retardant, a silane coupling agent, an antioxidant, a foam stabilizer, an ultraviolet absorber, a crosslinking agent, a catalyst, etc. by mechanical stirring and vacuum extraction.

[0014] Preferably, the weight ratio of the alkali-free continuous glass fiber to the thermosetting polyurethane rigid foam material in the profile is greater than 1:1.

[0015] The glass microbeads are used as fillers of the thermosetting polyurethane rigid foam resin to fill the pores formed by the polyurethane foam, thereby improving the compression strength of the polyurethane rigid foam resin without increasing the specific gravity of the material. The glass microbeads are hollow structures, and the bulk density is less than the free bubble density of the thermosetting polyurethane rigid foam material. The particle size of the glass microbeads is less than the pore diameter of the free bubble; preferably, the glass microbeads are micron-sized hollow glass microbeads with a particle size not greater than 70 microns and a bulk density of 0.2-0.25 g / cm 3 .

[0016] Another aspect of the present application provides a preparation method of a glass microbead modified polyurethane rigid foam composite profile, comprising the following operation steps:

[0017] Step one, the raw materials of thermosetting polyurethane hard foam material and glass beads are weighed and mixed, wherein the raw materials include polyether polyol a, polyether polyol b, flame retardant, foam stabilizer, silane coupling agent, antioxidant, ultraviolet absorber, crosslinking agent, catalyst, water and hollow glass microbeads;

[0018] Step two, another component of thermosetting polyurethane hard foam material modified isocyanate is weighed; the modified isocyanate is mixed with the raw materials mixed in step one and discharged to the mold;

[0019] Step three, the mold is preheated to 40-50℃, and the alkali-free continuous glass fiber is arranged;

[0020] Step four, the alkali-free continuous glass fiber mat is uniformly distributed in the material height direction.

[0021] Preferably, in the step one, the raw materials of each component are weighed according to the following weight ratio:

[0022] Polyether polyol a 80-120 parts;

[0023] Polyether polyol b 15-25 parts;

[0024] Flame retardant 8-12 parts;

[0025] Foam stabilizer 3-5 parts;

[0026] Silane coupling agent 0.5-3 parts;

[0027] Antioxidant 0.4-0.6 parts;

[0028] Ultraviolet absorber 0.4-0.6 parts;

[0029] Crosslinking agent 0.3-0.4 parts;

[0030] Catalyst 0.1-0.2 parts;

[0031] Water 0.2-0.4 parts;

[0032] Hollow glass microbeads 8-12 parts.

[0033] In order to more clearly embody the beneficial effects of the present application, the material properties and reinforcement principles of the present application are described as follows:

[0034] 1. The compression strength of the profile mainly depends on the compression strength of the thermosetting polyurethane hard foam material and the proportion of "reinforcing rib" (alkali-free continuous glass fiber); the larger the proportion of "reinforcing rib", the larger the material density and the compression strength, and the smaller the proportion of "reinforcing rib", the smaller the material density and the compression strength.

[0035] 2. For the same kind of thermosetting polyurethane rigid foam material, the compressive strength depends on the density of the resin free bubble, the free bubble density is high, the pore is small, the compressive strength is large, the free bubble density is low, the pore is large, the compressive strength is small.

[0036] 3. The alkali-free continuous glass fiber plays a role in improving the tensile strength in the length direction (longitudinal direction) of the profile, and the alkali-free continuous fiber glass felt plays a role in improving the tensile strength in the transverse direction of the material, thereby improving the shear resistance of the material. The more the number of layers of the felt, the stronger the shear resistance, but the resin permeability will be weakened.

[0037] Compared with the prior art, the beneficial effects of the present application are: by mixing hollow glass microspheres to fill the polyurethane foaming holes, since the bulk density of the hollow glass microspheres is less than the free bubble density, the overall weight of the polyurethane rigid foam mixed with the glass microspheres is lighter under the same compressive resistance; the more the glass microspheres mixed, the greater the improvement in the compressive strength of the product; the greater the areal density of the alkali-free continuous glass fiber felt, the more the number of layers, the stronger the shear resistance, but the resin permeability will be weakened accordingly; by appropriately adjusting the mixing ratio of the fiber and the resin, the uniformity of the distribution of the hollow glass microspheres with different mixing amounts in the profile is ensured; the composite profile provided by the technical scheme of the present application has the characteristics of low profile density and high compressive strength. BRIEF DESCRIPTION OF DRAWINGS

[0038] Figure 1 is a structure schematic view of the glass microsphere modified polyurethane rigid foam composite profile of the embodiment of the present application;

[0039] Figure 2 is Figure 1 a local enlarged structure schematic view of part of the area;

[0040] Marked: 1-alkali-free continuous glass fiber; 2-alkali-free continuous glass fiber felt; 3-thermosetting polyurethane rigid foam material; 4-glass microspheres. DETAILED DESCRIPTION

[0041] The specific embodiments of the present application will be further described in detail below in combination with the drawings and examples. The following examples are used to illustrate the present application, but not to limit the scope of the present application.

[0042] As Figures 1 to 2 shown, a glass microsphere modified polyurethane rigid foam composite profile of the present application includes alkali-free continuous glass fiber 1, alkali-free continuous glass fiber felt 2, thermosetting polyurethane rigid foam material 3 and glass microspheres 4. The alkali-free continuous glass fiber 1 is fixed inside the profile by the thermosetting polyurethane rigid foam material 3, the glass microspheres 4 are coated in the pores of the thermosetting polyurethane rigid foam material 3, and the alkali-free continuous glass fiber felt 2 is evenly embedded inside the profile.

[0043] Example 1

[0044] The respective raw materials are weighed according to the following proportions and mixed.

[0045] Polyether polyol a 100 parts

[0046] The polyether is a multifunctional low viscosity polyether obtained by polymerization of sucrose, glycerol as a starter and propylene oxide.

[0047] Polyether polyol b 20 parts

[0048] The polyether is a dihydric alcohol polyether obtained by sorbitol as a starter.

[0049] Flame retardant 10 parts

[0050] The flame retardant is a triphosphate containing both phosphorus and chlorine elements.

[0051] Cell stabilizer 4 parts

[0052] The cell stabilizer is a polysiloxane-polyether copolymer with a silicon-carbon structure.

[0053] Silane coupling agent 1 part

[0054] Antioxidant 0.5 parts

[0055] Ultraviolet absorber 0.5 parts

[0056] Crosslinking agent 0.35 parts

[0057] Catalyst 0.15 parts

[0058] Water 0.3 parts

[0059] Hollow glass microbeads 10 parts

[0060] The glass microbeads are micron-sized hollow glass microbeads with a particle size of not more than 70 microns and a bulk density of 0.2-0.25 g / cm 3 .

[0061] The raw materials are added to the mixing kettle in the above proportions in sequence, the mixing kettle is set to a temperature of 25°C, the temperature deviation is controlled to ±2°C, the stirring speed is 60 r / min, the vacuum degree is -0.09 Mpa, the vacuum degree control deviation is ±0.005 Mpa, and the stirring is carried out for 30 min; metering tank A is prepared for standby; the other component of the thermosetting polyurethane rigid foam material 3, modified isocyanate, is introduced into metering tank B for standby; the materials in metering tank A and metering tank B are mixed and discharged to the mold, and the weight ratio of the discharge of metering tank A and metering tank B is 1:1.

[0062] The mold is preheated, the mold temperature is set to 45℃, and the alkali-free continuous glass fiber is arranged. In this embodiment, the alkali-free continuous glass fiber 1 selected is a mixture of 19200 tex and 9600 tex, wherein the proportion of 19200 tex is 70%, and the proportion of 9600 tex is 30%; the mixing weight ratio of alkali-free continuous glass fiber 1 and thermosetting polyurethane rigid foam material 3 is 53:47; five layers of alkali-free continuous glass fiber felt 2 are uniformly distributed in the material height direction, and the area density is 300g / m 2 ; the upper and lower surfaces of the profile each have a layer of alkali-free continuous glass fiber felt 2; the alkali-free continuous glass fiber 1 is pressed and pulled by a track machine to ensure that the alkali-free continuous glass fiber 1 has a certain tension to improve the creep resistance of the material in the later stage.

[0063] Example 2

[0064] The corresponding raw materials of each component are weighed according to the following weight ratio and mixed.

[0065] Polyether polyol a 80 parts

[0066] The polyether is a multifunctional low-viscosity polyether obtained by polymerization of sucrose, glycerol as a starter and propylene oxide.

[0067] Polyether polyol b 15 parts

[0068] The polyether is a dihydric alcohol polyether with sorbitol as a starter.

[0069] Flame retardant 8 parts

[0070] The flame retardant is a triphosphate containing both phosphorus and chlorine elements.

[0071] Cell stabilizer 3 parts

[0072] The cell stabilizer is a polysiloxane-polyether copolymer with a silicon-carbon structure.

[0073] Silane coupling agent 0.5 parts

[0074] Antioxidant 0.4 parts

[0075] Ultraviolet absorber 0.4 parts

[0076] Crosslinking agent 0.3 parts

[0077] Catalyst 0.1 parts

[0078] Water 0.2 parts

[0079] Hollow glass beads 8 parts

[0080] The glass beads are micron-sized hollow glass beads, the particle size of the hollow glass beads is not greater than 70 microns, and the bulk density is 0.2-0.25g / cm 3 .

[0081] The raw materials are added into the mixing kettle in the above proportions in turn, the temperature of the mixing kettle is set to 25℃, the temperature deviation is controlled to ±2℃, the stirring speed is 60r / min, the vacuum degree is -0.09Mpa, the vacuum degree control deviation is ±0.005Mpa, stirring for 30min, and then the material is introduced into the metering tank A for standby; the other component of the thermosetting polyurethane rigid foam material 3, modified isocyanate, is introduced into the metering tank B for standby; the materials in the metering tank A and the metering tank B are mixed and discharged to the mold, and the weight ratio of the metering tank A and the metering tank B is 1:1.

[0082] The mold is preheated, and the mold temperature is set to 40℃. The alkali-free continuous glass fiber 1 is arranged, and the selected alkali-free continuous glass fiber 1 in this embodiment is a mixture of linear density 19200tex and 9600tex, wherein the proportion of 19200tex is 65%, and the proportion of 9600tex is 35%. The mixing weight ratio of the alkali-free continuous glass fiber 1 and the thermosetting polyurethane rigid foam material 3 is 52:48. Four layers of alkali-free continuous fiber felt are uniformly distributed in the material height direction, and the area density is 450g / m 2 ; there is one layer of alkali-free continuous glass fiber felt 2 on the upper and lower surfaces of the profile; the alkali-free continuous glass fiber 1 is pressed and pulled by a track machine to ensure that the alkali-free continuous glass fiber 1 has a certain tension to improve the creep resistance of the material in the later stage.

[0083] Example 3

[0084] The corresponding raw materials of each component are weighed according to the following weight ratio and mixed.

[0085] Polyether polyol a 120 parts

[0086] The polyether is a multifunctional low-viscosity polyether obtained by polymerization of sucrose, glycerol as a starter and propylene oxide.

[0087] Polyether polyol b 25 parts

[0088] The polyether is a dihydric alcohol polyether with sorbitol as a starter.

[0089] Flame retardant 12 parts

[0090] The flame retardant is a triphosphate containing both phosphorus and chlorine elements.

[0091] Cell stabilizer 5 parts

[0092] The cell stabilizer is a polysiloxane-polyether copolymer with a silicon-carbon structure.

[0093] Silane coupling agent 3 parts

[0094] Antioxidant 0.6 parts

[0095] Ultraviolet absorber 0.6 parts

[0096] Crosslinking agent 0.4 parts

[0097] Catalyst 0.2 parts

[0098] Water 0.4 parts

[0099] Hollow glass microbeads 20 parts

[0100] The glass microbeads are micron-sized hollow glass microbeads, the particle size of the hollow glass microbeads is not greater than 70 microns, and the bulk density is 0.2-0.25 g / cm 3 .

[0101] The raw materials are sequentially added to the mixing kettle in the above proportions, the mixing kettle is set to a temperature of 25 DEG C, the temperature deviation is controlled to be +2 DEG C, the stirring speed is 60 r / min, the vacuum degree is-0.09 Mpa, the vacuum degree control deviation is +0.005 Mpa, stirring is carried out for 30 min, and the material in metering tank A is reserved; the other component of the thermosetting polyurethane rigid foam material 3, modified isocyanate, is introduced into metering tank B for reservation; the materials in metering tank A and metering tank B are mixed and discharged to the mold, and the weight ratio of the discharge of metering tank A and metering tank B is 1:1.

[0102] The mold is preheated, the mold temperature is set to 50 DEG C, and the alkali-free continuous glass fiber is arranged, the alkali-free continuous glass fiber 1 selected in the embodiment is a mixture of linear density 2400 tex and 9600 tex, wherein the proportion of 2400 tex is 50%, and the proportion of 9600 tex is 50%; the mixing weight ratio of the alkali-free continuous glass fiber 1 and the thermosetting polyurethane rigid foam material 3 is 55:45. Three layers of alkali-free continuous fiber felt are uniformly distributed in the material height direction, and the surface density is 400 g / m 2 ; there is one layer of alkali-free continuous glass fiber felt 2 on the upper and lower surfaces of the profile; the alkali-free continuous glass fiber 1 is pressed and pulled by a caterpillar machine to ensure that the alkali-free continuous glass fiber 1 has a certain tension to improve the creep resistance of the material in the later stage.

[0103] The above only describes the preferred embodiments of the present application, and it should be noted that for ordinary skilled persons in the technical field, several improvements and modifications can be made without departing from the technical principles of the present application, and these improvements and modifications should also be considered as the protection scope of the present application.

Claims

1. A method for preparing a glass microsphere modified polyurethane rigid foam composite profile, characterized in that, The glass microsphere modified polyurethane rigid foam composite profile includes alkali-free continuous glass fiber (1), alkali-free continuous glass fiber mat (2), thermosetting polyurethane rigid foam material (3) and glass microsphere (4), the alkali-free continuous glass fiber (1) is fixed in the profile by the thermosetting polyurethane rigid foam material (3), the thermosetting polyurethane rigid foam material (3) is coated with glass microsphere (4) in the pore, and the alkali-free continuous glass fiber mat (2) is uniformly embedded in the profile; The alkali-free continuous glass fiber mat (2) is uniformly distributed in the composite profile in the pressure direction of the profile; At least one layer of alkali-free continuous glass fiber mat (2) is arranged on the upper and lower surfaces of the profile; The thermosetting polyurethane rigid foam material (3) is a two-component polyurethane resin composed of modified isocyanate and combined polyether polyol, wherein the combined polyether polyol is mixed by two polyether polyols, flame retardant, silane coupling agent, antioxidant, foam stabilizer, ultraviolet absorber, crosslinking agent and catalyst; The preparation method comprises the following operation steps: Step one, the raw materials of thermosetting polyurethane rigid foam material (3) and glass microsphere (4) are weighed according to the weight ratio and mixed and stirred, wherein the raw materials include polyether polyol a, polyether polyol b, flame retardant, foam stabilizer, silane coupling agent, antioxidant, ultraviolet absorber, crosslinking agent, catalyst, water and hollow glass microsphere; Step two, another component of the thermosetting polyurethane rigid foam material (3), modified isocyanate, is weighed; the modified isocyanate and the raw materials mixed in step one are mixed and discharged into the mold; Step three, the mold is preheated to 40-50℃, and the alkali-free continuous glass fiber is arranged; Step four, the alkali-free continuous glass fiber mat (2) is uniformly distributed in the material height direction.

2. The method for preparing the glass microsphere-modified polyurethane rigid foam composite profile as described in claim 1, characterized in that, The alkali-free continuous glass fiber (1) is a mixture of one or more linear density fibers, and has a certain traction tension before being mixed with the thermosetting polyurethane rigid foam material (3).

3. The method for preparing the glass microsphere-modified polyurethane rigid foam composite profile as described in claim 2, characterized in that, The interlayer structure formed by the alkali-free continuous glass fiber mat (2) is not less than 2 layers and not more than 6 layers.

4. The method for preparing the glass microsphere-modified polyurethane rigid foam composite profile as described in claim 1, characterized in that, The glass microsphere (4) is a hollow structure, and the bulk density is less than the free foam density of the thermosetting polyurethane rigid foam material (3), and the particle size of the glass microsphere (4) is less than the pore diameter of the free foam.

5. The method for preparing the glass microsphere-modified polyurethane rigid foam composite profile as described in claim 1, characterized in that, The weight ratio of the alkali-free continuous glass fiber (1) to the thermosetting polyurethane rigid foam material (3) in the profile is greater than 1:

1.

6. The method for preparing the glass microsphere-modified polyurethane rigid foam composite profile as described in claim 1, characterized in that, In step one, the raw materials are weighed according to the following weight ratio: Polyether polyol a 80-120 parts; Polyether polyol b 15-25 parts; Flame retardant 8-12 parts; Foam stabilizer 3-5 parts; Silane coupling agent 0.5-3 parts; Antioxidant 0.4-0.6 parts; Ultraviolet absorber 0.4-0.6 parts; Crosslinking agent 0.3-0.4 parts; Catalyst 0.1-0.2 parts; Water 0.2-0.4 parts; Hollow glass microsphere 8-20 parts.

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