CN113861711A - Wood-plastic composite section with low aging and fading speed and preparation method thereof - Google Patents
Wood-plastic composite section with low aging and fading speed and preparation method thereof Download PDFInfo
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- CN113861711A CN113861711A CN202111073622.3A CN202111073622A CN113861711A CN 113861711 A CN113861711 A CN 113861711A CN 202111073622 A CN202111073622 A CN 202111073622A CN 113861711 A CN113861711 A CN 113861711A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/02—Lignocellulosic material, e.g. wood, straw or bagasse
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention relates to the field of wood-plastic materials, in particular to a wood-plastic composite section with low aging and fading speed and a preparation method thereof, wherein the wood-plastic composite section comprises the following components: 100 parts of wood powder, 30-50 parts of polymer resin base material, 5-10 parts of toughening resin, 10-15 parts of modified rutile titanium dioxide, 10-15 parts of inorganic filler and 0-2 parts of auxiliary agent; the modified rutile type titanium dioxide is obtained by grafting and modifying a surface polymer chain segment of conventional rutile type titanium dioxide, wherein the polymer chain segment contains an ultraviolet absorbing group. The invention aims to overcome the defect of poor ultraviolet resistance of the wood-plastic composite material in the prior art, and the wood-plastic composite section has good ultraviolet resistance, so that the wood-plastic composite section has low aging and fading speed, the service life of the wood-plastic composite section is prolonged, the addition amount of an ultraviolet resistant agent is reduced, and the manufacturing cost of the wood-plastic composite section is reduced.
Description
Technical Field
The invention relates to the field of wood-plastic materials, in particular to a wood-plastic composite section with low aging and fading speeds and a preparation method thereof.
Background
In the existing wood-plastic composite materials (outdoors) on the market, in case of being applied outdoors, most of the wood-plastic composite materials are added with auxiliaries such as an anti-ultraviolet agent to slow down the aging, but the auxiliaries are expensive and have limited addition amount.
In addition, because the wood-plastic composite material needs different colors to meet the requirements of different customers, a certain amount of titanium dioxide is added more or less, the titanium dioxide has two forms, one is anatase type, the other is rutile type, and most of the added titanium dioxide is anatase type due to the need of controlling the cost, but the titanium dioxide in the form has certain activity, and the aging and the fading of the wood-plastic composite material can be accelerated under the irradiation of ultraviolet light. Although the factory cost of the wood-plastic products can be reduced, later complaints and compensation are often more huge and cannot be paid. Therefore, most wood plastic manufacturers may not be concerned with this.
The rutile titanium dioxide is inactive under general conditions, so that the aging of the composite material is not accelerated under the irradiation of ultraviolet light, and the service life of the wood-plastic composite material can be relatively delayed. However, rutile type titanium dioxide is doped with a trace amount of anatase type titanium dioxide in the preparation process, and a part of crystal lattices in rutile type titanium dioxide may have lattice defects, so that a certain amount of photoactivation points still exist. Therefore, for the reasons mentioned above, although rutile titanium dioxide has a significant advantage compared to anatase titanium dioxide, it still has a potential for further improvement.
The application number CN201110268259.0 provides a high-weather-resistance wood-like skinning foaming material with high hardness, good toughness, high weather resistance and low cost. The titanium dioxide and the ultraviolet absorbent are added into the conventional foaming material, so that the strong weather resistance and thermal stability of the rutile titanium dioxide are fully utilized, and the excellent thermal stability, chemical stability and light stability of the ultraviolet absorbent are utilized in combination in the foaming material, so that the thermal instability of PVC can be effectively reduced, and the weather resistance of the foaming material is improved. The wood-imitating effect can be achieved by blending the organic or inorganic toner, the appearance of the wood-imitating wood is enhanced, the environment is protected, and the danger in the processes of production, use and the like is reduced.
Disclosure of Invention
The invention provides a wood-plastic composite section with low aging and fading speeds and a preparation method thereof, aiming at overcoming the defect that the ultraviolet resistance of a wood-plastic material in the prior art is poor, so that the outdoor aging resistance is poor.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a wood-plastic composite profile with low aging fade rate, comprising: 100 parts of wood powder, 30-50 parts of polymer resin base material, 5-10 parts of toughening resin, 10-15 parts of modified rutile titanium dioxide, 10-15 parts of inorganic filler and 0-2 parts of auxiliary agent;
the modified rutile type titanium dioxide is obtained by grafting and modifying a surface polymer chain segment of conventional rutile type titanium dioxide, wherein the polymer chain segment contains an ultraviolet absorbing group.
In order to improve the ultraviolet resistance of the conventional wood-plastic section, a certain amount of ultraviolet resistant agent is usually added in the conventional wood-plastic section, and the ultraviolet resistance of the conventional wood-plastic section is generally in direct proportion to the addition amount of the ultraviolet resistant agent, so that the wood-plastic material has better ultraviolet resistance and weather resistance, and the addition amount of the ultraviolet resistant agent is usually higher. Since the price of the anti-ultraviolet agent is expensive, the cost of the wood-plastic material with good anti-ultraviolet performance is usually higher.
In addition, although the addition of the anti-ultraviolet agent can obviously improve the anti-ultraviolet performance of the wood-plastic material, the anti-ultraviolet agent is usually added in a monomer form, so that the anti-ultraviolet agent on the surface layer of the wood-plastic material can be gradually precipitated under the action of long-time cold and hot water and rainwater and sunlight, and the anti-ultraviolet capability of the surface layer of the material is gradually reduced. Therefore, after long-term use, the surface layer of the wood-plastic material can be faded, even pulverized and broken due to precipitation of the anti-ultraviolet agent, and the aesthetic property and the mechanical property of the wood-plastic material are seriously affected. Meanwhile, after the surface layer is damaged, corresponding problems can occur inside the wood-plastic material gradually.
According to the wood-plastic section bar, the ultraviolet absorption groups with the ultraviolet resistance effect are connected in the polymer chain segment, and the polymer chain segment is grafted and connected with the rutile titanium dioxide, so that the ultraviolet absorption groups are fixed, the ultraviolet absorption groups cannot be separated out in the daily use process, the ultraviolet resistance performance cannot be reduced, the weather resistance of the wood-plastic section bar is greatly improved, the service life of the wood-plastic section bar is prolonged, and the phenomena of color fading, pulverization and breakage cannot occur in the outdoor use process.
Meanwhile, as the ultraviolet absorbing group is fixed by rutile titanium dioxide and a polymer chain segment, the lasting ultraviolet resistance of the ultraviolet absorbing group can be ensured under the condition of low addition amount, so that the cost for achieving stronger ultraviolet resistance can be greatly reduced.
In addition, the polymer chain segment with the ultraviolet absorption group can play a role in shielding rutile titanium dioxide, so that the optical activity of trace anatase titanium dioxide doped in the rutile titanium dioxide and a part of titanium dioxide with lattice defects is greatly weakened, and the ultraviolet resistance of the titanium dioxide is further improved.
Preferably, the surface modification method of the modified rutile type titanium dioxide comprises the following steps:
(1) uniformly spraying a silane coupling agent prehydrolysis solution containing acryloyloxy groups into the rutile titanium dioxide, uniformly mixing, and drying to obtain the rutile titanium dioxide with the surface group modified, wherein the reaction formula is shown as the following formula (1):
formula (1).
(2) Reacting 4,4' -dihydroxy benzophenone with acryloyl chloride to obtain a polymeric monomer A with a benzophenone structure, wherein the reaction scheme is shown as the following formula (2):
formula (2).
(3) Dispersing rutile type titanium dioxide modified by surface groups, methyl acrylate and a polymeric monomer A in an organic solution, polymerizing for a certain time by free radicals under the action of an initiator, evaporating to remove a solvent after the reaction is finished, washing and drying to obtain the rutile type titanium dioxide modified by polymer grafting on the surface, wherein the reaction formula is shown as the following formula (3):
formula (3).
The surface of rutile titanium dioxide is generally provided with a certain amount of active hydroxyl groups, so that acryloxy groups can be grafted to the surface of rutile titanium dioxide by reacting these active hydroxyl groups with a prehydrolysis solution of a silane coupling agent containing acryloxy groups, so that there is a possibility of further modification. The prehydrolysis solution of the silane coupling agent is adopted to react with the titanium dioxide, and the reason is that the number of active silicon hydroxyl groups of the prehydrolyzed silane coupling agent is greatly increased, so that the reaction probability of the silane coupling agent with the hydroxyl groups on the surface of the titanium dioxide is greatly increased, and the corresponding grafting rate is improved.
The polymer A contains a benzophenone structure, has good uvioresistant performance, can form the polymer A with two acryloyloxy groups after reacting with acryloyl chloride, and obtains a polymer chain segment with the uvioresistant performance through solution polymerization after compounding the polymer A and methyl acrylate, so that the wood-plastic material achieves the uvioresistant effect and cannot fade rapidly under the irradiation of sunlight.
Meanwhile, the polymer chain segment in the invention has a polar acrylate structure, so that the compatibility with wood flour can be improved, and the polymer chain segment can be used as a coupling agent to improve the compatibility with components. After several experiments, the inventors have also surprisingly found that by using rutile titanium dioxide grafted with polymer segments, the conditions for the preparation of the monolith can be made more moderate, in particular with a significant drop in the granulation and extrusion temperatures.
Preferably, the silane coupling agent prehydrolysis solution in step (1) is prepared as follows: dissolving a silane coupling agent containing acryloyloxy into an ethanol water solution, and stirring for 1-3 hours at 35-55 ℃ to obtain a silane coupling agent prehydrolysis solution;
wherein: the adhesive comprises, by mass, 20-30% of a silane coupling agent containing acryloxy groups, 30-50% of ethanol and the balance of water.
More preferably, the acryloxy group-containing silane coupling agent is any one of γ -methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriisopropoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, and 3-methacryloxypropyltriethoxysilane.
Preferably, the mass ratio of the rutile titanium dioxide to the silane coupling agent prehydrolysis solution is 100: (5-15).
Preferably, the mass ratio of the rutile type titanium dioxide with modified surface groups, the methyl acrylate and the polymerized monomer A in the step (3) is 100: (10-15): (1-5).
Preferably, the polymer resin substrate includes polyethylene, polypropylene, polystyrene, polycarbonate, acrylonitrile-butadiene-styrene terpolymer, polyvinyl chloride.
Preferably, the toughening resin comprises a composition of one or more of EPDM-g-MAH, EPDM-g-GMA, PP-g-MAH, PP-g-GMA, PE-g-MAH, PE-g-GMA, POE-g-MAH, POE-g-GMA, EMA-g-MAH, EBA-g-GMA, EBA-g-MAH and SEBS-g-MAH as a toughening agent.
Preferably, the inorganic filler comprises one or more of calcium carbonate, white carbon black, talcum powder, calcium sulfate and barium sulfate.
Preferably, the auxiliary agent comprises one of an antioxidant, a lubricant and a stabilizer.
A preparation method of a wood-plastic composite section with low aging and fading speeds comprises the following steps: weighing the components of the wood-plastic composite section, uniformly mixing, granulating to obtain granules, and performing extrusion molding on the granules through an extruder to obtain the wood-plastic section.
Therefore, the invention has the following beneficial effects:
(1) the wood-plastic composite section has good ultraviolet resistance, so that the wood-plastic composite section has low aging and fading speed, and the service life of the wood-plastic composite section is prolonged;
(2) the addition amount of the anti-ultraviolet agent is reduced, and the manufacturing cost of the wood-plastic composite section is reduced;
(3) the temperature required during granulation and extrusion can be effectively reduced.
Detailed Description
The invention is further described with reference to specific examples. Those skilled in the art will be able to implement the invention based on these teachings. Moreover, the embodiments of the present invention described in the following description are generally only some embodiments of the present invention, and not all embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
The preparation method of the modified rutile type titanium dioxide (A1) comprises the following steps:
(1) uniformly spraying a gamma-methacryloxypropyltrimethoxysilane prehydrolysis solution accounting for 5 percent of the mass of the rutile titanium dioxide into the rutile titanium dioxide, uniformly mixing, and drying to obtain the rutile titanium dioxide with surface group modification;
the configuration of the prehydrolysis solution is as follows: weighing gamma-methacryloxypropyltrimethoxysilane, ethanol and water in sequence according to the mass ratio of 20/30/50, mixing, and stirring for 3 hours at the temperature of 35 ℃ to obtain the silane coupling agent prehydrolysis solution.
(2) After 2.14g of 4,4' -dihydroxybenzophenone (0.01 mol) and 2.02g of triethylamine (0.02 mol) were dissolved in 50ml of dichloromethane, a mixture of 1.81g of acryloyl chloride (0.02 mol) and 20ml of dichloromethane was added dropwise at-10 ℃ to react for 3 hours, the triethylamine hydrochloride salt was removed by filtration, the filtrate was washed with water, and the solvent was distilled off to obtain a polymer monomer A having a benzophenone structure.
(3) 10g of rutile type titanium dioxide with modified surface groups, 1g of methyl acrylate and 0.1g of polymeric monomer A are dispersed in 50ml of toluene, 0.05g of AIBN is added, the temperature is raised to 65 ℃, free radical polymerization is carried out for 5h, after the reaction is finished, the solvent is evaporated, and the rutile type titanium dioxide with the modified surface through polymer grafting is obtained by washing and drying (A1).
The mass percentage of the benzophenone structure in the rutile type titanium dioxide (A1) is 0.55 percent.
Secondly, the surface modification method of the modified rutile type titanium dioxide (A2) is as follows:
(1) uniformly spraying 3-methacryloxypropyltriethoxysilane prehydrolysis solution with the mass of 10% of that of the rutile titanium dioxide into the rutile titanium dioxide, uniformly mixing, and drying to obtain surface group modified rutile titanium dioxide;
the configuration of the prehydrolysis solution is as follows: 3-methacryloxypropyltriethoxysilane, ethanol and water are sequentially weighed according to the mass ratio of 25/40/35, and are mixed and stirred for 2 hours at the temperature of 50 ℃ to obtain the silane coupling agent prehydrolysis solution.
(2) 10g of rutile titanium dioxide with modified surface groups, 1.5g of methyl acrylate and 0.3g of polymerized monomer A are dispersed in 50ml of toluene, 0.05g of AIBN is added, the temperature is raised to 65 ℃, free radical polymerization is carried out for 5h, after the reaction is finished, the solvent is distilled off, and the rutile titanium dioxide with the modified surface through polymer grafting is obtained by washing and drying (A2).
The mass percent of the benzophenone structure in the rutile type titanium dioxide (A2) is 1.54%.
The preparation method of the (III) modified rutile type titanium dioxide (A3) comprises the following steps:
(1) uniformly spraying a 3-methacryloxypropyl triisopropoxysilane prehydrolysis solution accounting for 15 percent of the mass of the rutile titanium dioxide into the rutile titanium dioxide, uniformly mixing, and drying to obtain the rutile titanium dioxide with surface group modification;
the configuration of the prehydrolysis solution is as follows: 3-methacryloxypropyl triisopropoxy silicon, ethanol and water are sequentially weighed according to the mass ratio of 30/50/20, and are mixed and stirred for 1h at the temperature of 55 ℃ to obtain the silane coupling agent prehydrolysis solution.
(2) 10g of rutile titanium dioxide with modified surface groups, 1.2g of methyl acrylate and 0.5g of polymerized monomer A are dispersed in 50ml of toluene, 0.05g of AIBN is added, the temperature is raised to 65 ℃, free radical polymerization is carried out for 5h, after the reaction is finished, the solvent is distilled off, and the rutile titanium dioxide with the modified surface through polymer grafting is obtained by washing and drying (A3).
The mass percentage of the benzophenone structure in the rutile type titanium dioxide (A3) was 2.59%.
Example 1
A wood-plastic composite profile with low aging fade rate, comprising: 100 parts of wood powder, 45 parts of polyethylene, 6 parts of PE-g-MAH, 1 part of POE-g-MAH, 10 parts of modified rutile titanium dioxide (A1), 12 parts of calcium carbonate and 1 part of lubricant.
A preparation method of a wood-plastic composite section with low aging and fading speeds comprises the following steps: weighing the components of the wood-plastic composite section, uniformly mixing, adding into a hopper of a granulator, granulating at 160 ℃ to obtain granules, adding the granules into the hopper of an extruder, controlling the extrusion temperature to 140 ℃, and performing extrusion molding to obtain the wood-plastic section.
Example 2
A wood-plastic composite profile with low aging fade rate, comprising: 100 parts of wood powder, 45 parts of polyethylene, 6 parts of PE-g-MAH, 1 part of POE-g-MAH, 12 parts of modified rutile titanium dioxide (A1), 12 parts of calcium carbonate and 1 part of lubricant.
A preparation method of a wood-plastic composite section with low aging and fading speeds comprises the following steps: weighing the components of the wood-plastic composite section, uniformly mixing, adding into a hopper of a granulator, granulating at 160 ℃ to obtain granules, adding the granules into the hopper of an extruder, controlling the extrusion temperature to 140 ℃, and performing extrusion molding to obtain the wood-plastic section.
Example 3
A wood-plastic composite profile with low aging fade rate, comprising: 100 parts of wood powder, 45 parts of polyethylene, 6 parts of PE-g-MAH, 1 part of POE-g-MAH, 15 parts of modified rutile titanium dioxide (A1), 12 parts of calcium carbonate and 1 part of lubricant.
A preparation method of a wood-plastic composite section with low aging and fading speeds comprises the following steps: weighing the components of the wood-plastic composite section, uniformly mixing, adding into a hopper of a granulator, granulating at 160 ℃ to obtain granules, adding the granules into the hopper of an extruder, controlling the extrusion temperature to 140 ℃, and performing extrusion molding to obtain the wood-plastic section.
Example 4
A wood-plastic composite profile with low aging fade rate, comprising: 100 parts of wood powder, 45 parts of polyethylene, 6 parts of PE-g-MAH, 1 part of POE-g-MAH, 12 parts of modified rutile titanium dioxide (A2), 12 parts of calcium carbonate and 1 part of lubricant.
A preparation method of a wood-plastic composite section with low aging and fading speeds comprises the following steps: weighing the components of the wood-plastic composite section, uniformly mixing, adding into a hopper of a granulator, granulating at 160 ℃ to obtain granules, adding the granules into the hopper of an extruder, controlling the extrusion temperature to 140 ℃, and performing extrusion molding to obtain the wood-plastic section.
Example 5
A wood-plastic composite profile with low aging fade rate, comprising: 100 parts of wood powder, 45 parts of polyethylene, 6 parts of PE-g-MAH, 1 part of POE-g-MAH, 12 parts of modified rutile titanium dioxide (A3), 12 parts of calcium carbonate and 1 part of lubricant.
A preparation method of a wood-plastic composite section with low aging and fading speeds comprises the following steps: weighing the components of the wood-plastic composite section, uniformly mixing, adding into a hopper of a granulator, granulating at 160 ℃ to obtain granules, adding the granules into the hopper of an extruder, controlling the extrusion temperature to 140 ℃, and performing extrusion molding to obtain the wood-plastic section.
Example 6
A wood-plastic composite profile with low aging fade rate, comprising: 100 parts of wood powder, 30 parts of polyethylene, 5 parts of EPDM-g-MAH, 12 parts of modified rutile titanium dioxide (A2), 10 parts of white carbon black, 1 part of antioxidant and 1 part of lubricant.
A preparation method of a wood-plastic composite section with low aging and fading speeds comprises the following steps: weighing the components of the wood-plastic composite section, uniformly mixing, adding into a hopper of a granulator, granulating at 160 ℃ to obtain granules, adding the granules into the hopper of an extruder, controlling the extrusion temperature to 140 ℃, and performing extrusion molding to obtain the wood-plastic section.
Example 7
A wood-plastic composite profile with low aging fade rate, comprising: 100 parts of wood powder, 50 parts of polyethylene, 6 parts of PE-g-MAH, 3 parts of POE-g-MAH, 15 parts of modified rutile titanium dioxide (A1), 15 parts of talcum powder and 0.5 part of antioxidant.
A preparation method of a wood-plastic composite section with low aging and fading speeds comprises the following steps: weighing the components of the wood-plastic composite section, uniformly mixing, adding into a hopper of a granulator, granulating at 160 ℃ to obtain granules, adding the granules into the hopper of an extruder, controlling the extrusion temperature to 140 ℃, and performing extrusion molding to obtain the wood-plastic section.
Example 8
A wood-plastic composite profile with low aging fade rate, comprising: 100 parts of wood powder, 35 parts of polyethylene, 3 parts of PE-g-MAH, 2 parts of POE-g-MAH, 12 parts of modified rutile titanium dioxide (A2), 12 parts of barium sulfate and 0.5 part of lubricant.
A preparation method of a wood-plastic composite section with low aging and fading speeds comprises the following steps: weighing the components of the wood-plastic composite section, uniformly mixing, adding into a hopper of a granulator, granulating at 160 ℃ to obtain granules, adding the granules into the hopper of an extruder, controlling the extrusion temperature to 140 ℃, and performing extrusion molding to obtain the wood-plastic section.
Example 9
A wood-plastic composite profile with low aging fade rate, comprising: 100 parts of wood powder, 40 parts of polypropylene, 5 parts of PP-g-MAH, 2 parts of POE-g-MAH, 15 parts of modified rutile titanium dioxide (A1) and 15 parts of calcium carbonate.
A preparation method of a wood-plastic composite section with low aging and fading speeds comprises the following steps: weighing the components of the wood-plastic composite section, uniformly mixing, adding into a hopper of a granulator, granulating at 160 ℃ to obtain granules, adding the granules into the hopper of an extruder, controlling the extrusion temperature to 140 ℃, and performing extrusion molding to obtain the wood-plastic section.
Example 10
A wood-plastic composite profile with low aging fade rate, comprising: 100 parts of wood powder, 45 parts of polystyrene, 2 parts of EMA-g-MAH, 4 parts of POE-g-MAH, 13 parts of modified rutile titanium dioxide (A3), 12 parts of calcium carbonate, 1.5 parts of antioxidant and 0.5 part of lubricant.
A preparation method of a wood-plastic composite section with low aging and fading speeds comprises the following steps: weighing the components of the wood-plastic composite section, uniformly mixing, adding into a hopper of a granulator, granulating at 160 ℃ to obtain granules, adding the granules into the hopper of an extruder, controlling the extrusion temperature to 140 ℃, and performing extrusion molding to obtain the wood-plastic section.
Example 11
A wood-plastic composite profile with low aging fade rate, comprising: 100 parts of wood powder, 45 parts of polyvinyl chloride, EPDM-g-MAH5 parts, 2 parts of POE-g-GMA, 14 parts of modified rutile titanium dioxide (A3), 12 parts of calcium carbonate and 2 parts of antioxidant.
A preparation method of a wood-plastic composite section with low aging and fading speeds comprises the following steps: weighing the components of the wood-plastic composite section, uniformly mixing, adding into a hopper of a granulator, granulating at 165 ℃ to obtain granules, adding the granules into the hopper of an extruder, controlling the extrusion temperature to 145 ℃, and performing extrusion molding to obtain the wood-plastic section.
The formulation of each component of examples 1-11 is shown in table 1 below:
TABLE 1 proportioning Table for each example
Comparative example 1
A wood-plastic composite profile, comprising: 100 parts of wood powder, 45 parts of polyethylene, 6 parts of PE-g-MAH, 1 part of POE-g-MAH, 12 parts of rutile titanium dioxide, 12 parts of calcium carbonate, 2 parts of 4,4' -dihydroxy benzophenone and 1 part of lubricant.
The preparation method of the wood-plastic composite section comprises the following steps: weighing the components of the wood-plastic composite section, uniformly mixing, adding into a hopper of a granulator, granulating at 190 ℃ to obtain granules, adding the granules into the hopper of an extruder, controlling the extrusion temperature to 165 ℃, and performing extrusion molding to obtain the wood-plastic section.
Comparative example 2
A wood-plastic composite profile, comprising: 100 parts of wood powder, 45 parts of polyethylene, 6 parts of PE-g-MAH, 1 part of POE-g-MAH, 12 parts of rutile titanium dioxide, 12 parts of calcium carbonate, 5 parts of 4,4' -dihydroxy benzophenone and 1 part of lubricant.
The preparation method of the wood-plastic composite section comprises the following steps: weighing the components of the wood-plastic composite section, uniformly mixing, adding into a hopper of a granulator, granulating at 190 ℃ to obtain granules, adding the granules into the hopper of an extruder, controlling the extrusion temperature to 155 ℃, and performing extrusion molding to obtain the wood-plastic section.
Comparative example 3
The preparation method of the polymer with the benzophenone structure comprises the following steps: dispersing 1.2g of methyl acrylate and 0.5g of a polymeric monomer A in 50ml of toluene, adding 0.05g of AIBN, heating to 65 ℃, carrying out free radical polymerization for 5 hours, evaporating the solvent after the reaction is finished, washing with water, and drying to obtain a polymer with a benzophenone structure, wherein the mass percent of the benzophenone structure is 17.8%.
A wood-plastic composite profile, comprising: 100 parts of wood powder, 45 parts of polyethylene, 6 parts of PE-g-MAH, 1 part of POE-g-MAH, 12 parts of rutile titanium dioxide, 0.37 part of polymer with a benzophenone structure (the mass of the benzophenone structure is the same as that of the embodiment 2), 12 parts of calcium carbonate and 1 part of lubricant.
The preparation method of the wood-plastic composite section comprises the following steps: weighing the components of the wood-plastic composite section, uniformly mixing, adding into a hopper of a granulator, granulating at 185 ℃ to obtain granules, adding the granules into the hopper of an extruder, controlling the extrusion temperature to 160 ℃, and performing extrusion molding to obtain the wood-plastic section.
Comparative example 4
The formulation of the wood plastic composite profile of comparative example 4 is the same as that of comparative example 1, and the difference from comparative example 1 is that the granulation and extrusion temperatures during the preparation process are different.
The method comprises the following specific steps:
the preparation method of the wood-plastic composite section comprises the following steps: weighing the components of the wood-plastic composite section, uniformly mixing, adding into a hopper of a granulator, granulating at 160 ℃ to obtain granules, adding the granules into the hopper of an extruder, controlling the extrusion temperature to 140 ℃, and performing extrusion molding to obtain the wood-plastic section.
Comparative example 5
The formulation of the wood plastic composite profile of comparative example 5 is the same as that of comparative example 3, and the difference from comparative example 3 is that the granulation and extrusion temperatures during the preparation process are different.
The method comprises the following specific steps:
the preparation method of the wood-plastic composite section comprises the following steps: weighing the components of the wood-plastic composite section, uniformly mixing, adding into a hopper of a granulator, granulating at 160 ℃ to obtain granules, adding the granules into the hopper of an extruder, controlling the extrusion temperature to 140 ℃, and performing extrusion molding to obtain the wood-plastic section.
The proportions of the components of comparative examples 1 to 3 are shown in Table 2 below:
TABLE 2 proportioning table of each proportion
The wood-plastic profiles prepared in examples 1 to 11 and comparative examples 1 to 3 were subjected to aging and fading tests, the test methods are as follows:
the obtained wood-plastic floorings of examples 1 to 11 were respectively prepared into 1 piece of floorings of 2m in length, and divided into two, and then respectively numbered as example 1-1 and example 1-2, example 2-1 and example 2-2, and so on until example 11-1 and example 11-2.
The obtained comparative examples 1 to 3 were also each prepared as 1 floor of 2m length and divided into two, and then numbered as comparative example 1-1 and comparative example 1-2, comparative example 2-1 and comparative example 2-2, comparative example 3-1 and comparative example 3-2.
The examples 1-1, 2-1 and 3-1 were protected from light, while the examples 1-2, 2-2 and 3-2 were placed in areas where sunlight was directly available, and the hue difference Δ Ε from the original floor was measured once a month by a colorimeter, and was continuously measured for 6 months.
The test results are shown in table 3 below:
TABLE 3 age fade test results for each example and comparative example
| Numbering | Original Δ Ε | Δ Ε 1 month | Δ Ε at month 3 | Δ Ε at 6 months |
| Example 1 | 0.1 | 0.1 | 0.5 | 1.3 |
| Example 2 | 0.1 | 0.1 | 0.4 | 1.1 |
| Example 3 | 0.1 | 0.1 | 0.3 | 0.9 |
| Example 4 | 0.1 | 0.1 | 0.3 | 0.9 |
| Example 5 | 0.1 | 0.1 | 0.2 | 0.7 |
| Example 6 | 0.1 | 0.1 | 0.3 | 1.0 |
| Example 7 | 0.1 | 0.1 | 0.4 | 1.0 |
| Example 8 | 0.1 | 0.1 | 0.3 | 0.8 |
| Example 9 | 0.1 | 0.1 | 0.4 | 0.9 |
| Example 10 | 0.1 | 0.1 | 0.2 | 0.9 |
| Example 11 | 0.1 | 0.1 | 0.3 | 1.0 |
| Comparative example1 | 0.1 | 1.2 | 5.6 | 12.8 |
| Comparative example 2 | 0.1 | 0.6 | 2.2 | 8.6 |
| Comparative example 3 | 0.1 | 0.4 | 1.8 | 5.2 |
Note: the color difference meter is a portable 3nh Sanenz color difference meter.
As is apparent from an examination of the composition tables of example 2 and comparative examples 1 to 2, the content of the ultraviolet absorbing group in example 2 was about 0.066 parts, as converted to 4,4 '-dihydroxybenzophenone, while the amount of 4,4' -dihydroxybenzophenone added in comparative example 1 was 2 parts, and the amount of 4,4 '-dihydroxybenzophenone added in comparative example 2 was 5 parts, so that the amount of 4,4' -dihydroxybenzophenone added was much larger in both comparative example 1 and comparative example 2 than in example 2. However, as can be seen from the aging fading test result table, the aging fading resistant effect in example 2 is much better than that in comparative example 1 and comparative example 2, so that it is proved that the technical scheme of the invention can realize good and durable ultraviolet resistance under the condition of adding the ultra-low ultraviolet resistant agent, and effectively prolong the outdoor service life of the floor.
Meanwhile, comparing example 2 and comparative example 3, the difference between the two is that the rutile type titanium dioxide powder in example 2 is grafted with a polymer segment containing an ultraviolet absorbing group on the surface, while comparative example 3 is that the polymer containing an ultraviolet absorbing group is added into the system separately and is not grafted with the surface of the rutile type titanium dioxide powder, and the ultraviolet absorbing group content of the two is the same by calculation. However, as is clear from the aging discoloration test result table, the aging discoloration resistance effect in example 2 is also better than that in comparative example 3. The technical scheme of the invention shows that the polymer chain segment with the ultraviolet absorption group can shield the rutile type titanium dioxide, so that the optical activity of trace anatase type titanium dioxide doped in the rutile type titanium dioxide and a part of titanium dioxide with lattice defects is greatly weakened, and the ultraviolet resistance of the titanium dioxide is further improved.
Comparing examples 1-3, we find that the only difference between the three is the change of the content of the ultraviolet absorbing group, which indicates that the uvioresistant performance is in direct proportion to the content of the ultraviolet absorbing group. This rule can also be derived from a comparison between example 2, example 4 and example 5.
In addition, we compared the surface morphology of the profiles prepared at five different forming temperatures of example 2, comparative example 1, comparative example 3, comparative example 4 and comparative example 5 by visual inspection, and the results are shown in table 4 below.
TABLE 4 summary of apparent morphology
| Item | Surface morphology |
| Example 2 | The appearance is full without holes, and the finished product has good glossiness |
| Comparative example 1 | The appearance is full without holes, and the finished product has good glossiness |
| Comparative example 4 | The surface of the section bar has flow lines, the surface of an extruded product is rough, and the glossiness is poor |
| Comparative example 3 | The appearance is full without holes, and the finished product has good glossiness |
| Comparative example 5 | The surface of the section bar has flow lines, the surface of an extruded product is rough, and the glossiness is poor |
By summarizing the summary of surface morphology in the table above, we found that:
although the comparative examples 1 and 4 are the same in material ratio, the problems of flow marks on the surface and roughness of the finished product surface are caused by the lower granulation and forming temperature in the comparative example 4 (the conditions are the same as those in the inventive example 2), which indicates that the material has poor melting performance, and the apparent shape becomes full and has no holes after the temperature is raised to the temperature in the comparative example 1, the finished product has good gloss, which indicates that the component formulas in the comparative examples 1 and 4 are not suitable for profile manufacturing at the lower forming temperature.
Similarly, both comparative examples 3 and 5 are the same in material ratio, but the problems of flow marks on the surface and roughness of the finished product surface are caused by the lower granulation and forming temperature in the comparative example 5 (the conditions are the same as those in the inventive example 2), which indicates that the material has poor melting performance, and the apparent morphology becomes full and pore-free after the temperature is raised to the temperature in the comparative example 3, the finished product has good gloss, which indicates that the component formulas in the comparative examples 3 and 5 are not suitable for profile manufacturing at the lower forming temperature.
In the embodiment 2 of the invention, after the surface polymer grafting modification is carried out on the rutile type titanium dioxide, the required granulation temperature and the base temperature are greatly reduced, and the profile prepared at the lower molding temperature is full in appearance, free of holes and good in finished product glossiness. The reason is presumed that the polymer grafting chain segment can improve the compatibility between the rutile titanium dioxide and the wood flour and the materials, so that the compatibility between the rutile titanium dioxide and the components can be improved as a bridging agent, the preparation conditions can be more moderate in the preparation process, the temperature required in the preparation process is reduced, and the apparent appearance of the product can reach the level which can be prepared only at higher temperature in the traditional method. The characteristic also meets the requirements of energy conservation and environmental protection, and the lower molding temperature can also prevent the material from being oxidized and denatured in the molding process, thereby being beneficial to improving the quality of the section.
Claims (10)
1. A wood-plastic composite profile with low aging and fading speed is characterized by comprising: 100 parts of wood powder, 30-50 parts of polymer resin base material, 5-10 parts of toughening resin, 10-15 parts of modified rutile titanium dioxide, 10-15 parts of inorganic filler and 0-5 parts of auxiliary agent;
the modified rutile type titanium dioxide is obtained by grafting and modifying a surface polymer chain segment of conventional rutile type titanium dioxide, wherein the polymer chain segment contains an ultraviolet absorbing group.
2. The wood-plastic composite profile with low aging and fading speed as claimed in claim 1, wherein the surface modification method of the modified rutile type titanium dioxide comprises the following steps:
(1) uniformly spraying a silane coupling agent prehydrolysis solution containing acryloyloxy groups into the rutile titanium dioxide, uniformly mixing, and drying to obtain surface group modified rutile titanium dioxide;
(2) reacting 4,4' -dihydroxy benzophenone with acryloyl chloride to obtain a polymeric monomer A with a benzophenone structure;
(3) dispersing the rutile type titanium dioxide with the modified surface groups, methyl acrylate and a polymeric monomer A in an organic solution, polymerizing for a certain time by free radicals under the action of an initiator, evaporating to remove a solvent after the reaction is finished, washing and drying to obtain the rutile type titanium dioxide with the modified surface by polymer grafting.
3. The wood-plastic composite profile with low aging fading speed as claimed in claim 2, wherein the silane coupling agent prehydrolysis solution in the step (1) is prepared as follows: dissolving a silane coupling agent containing acryloyloxy into an ethanol water solution, and stirring for 1-3 hours at 35-55 ℃ to obtain a silane coupling agent prehydrolysis solution;
wherein: the adhesive comprises, by mass, 20-30% of a silane coupling agent containing acryloxy groups, 30-50% of ethanol and the balance of water.
4. The wood-plastic composite profile with low aging fading speed as claimed in claim 2 or 3, wherein the mass ratio of the rutile type titanium dioxide to the silane coupling agent prehydrolysis solution is 100: (5-15).
5. The wood-plastic composite profile with low aging fading speed of claim 2, wherein the mass ratio of the surface group modified rutile type titanium dioxide, the methyl acrylate and the polymerized monomer A in the step (3) is 100: (10-15): (1-5).
6. A wood-plastic composite profile with low aging fade rate according to claim 1, wherein the polymer resin matrix comprises polyethylene, polypropylene, polystyrene, polycarbonate, acrylonitrile-butadiene-styrene terpolymer, polyvinyl chloride.
7. The wood-plastic composite profile with low aging fading speed as claimed in claim 1, wherein the toughening resin comprises a composition of toughening agent being one or more of EPDM-g-MAH, EPDM-g-GMA, PP-g-MAH, PP-g-GMA, PE-g-MAH, PE-g-GMA, POE-g-MAH, POE-g-GMA, EMA-g-MAH, EBA-g-GMA, EBA-g-MAH, SEBS-g-MAH.
8. A wood-plastic composite profile with low aging fading speed according to claim 1, wherein the inorganic filler comprises one or more of calcium carbonate, white carbon, talcum powder, calcium sulfate and barium sulfate.
9. The wood-plastic composite profile with low aging fading speed of claim 1, wherein the auxiliary agent comprises one or more of an antioxidant, a lubricant and a stabilizer.
10. The preparation method of the wood-plastic composite section with low aging and fading speeds is characterized by comprising the following steps: weighing the components of the wood-plastic composite section bar as defined in any one of claims 1 to 9, uniformly mixing, granulating to obtain granules, and performing extrusion molding on the granules through an extruder to obtain the wood-plastic section bar.
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