CN103224668B - A kind of polypropylene-base bamboo moulds the preparation method of foam composite material - Google Patents
A kind of polypropylene-base bamboo moulds the preparation method of foam composite material Download PDFInfo
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Abstract
The present invention discloses the preparation method that a kind of polypropylene-base bamboo moulds foam composite material, and this polypropylene-base bamboo is moulded foam composite material and acrylic resin, linking agent, additional crosslinker, whipping agent and blowing promotor are extruded producing foamed masterbatch through torque rheometer; Acrylic resin, lubricant, antioxidant, anti UV agent, bamboo powder, interfacial compatibilizer are heated up in high-speed mixer and mix, obtained Preblend, puts into torque rheometer banburying by Preblend, well-thought-out plan plastic particles is pulverized in discharging; Being mixed with foaming concentrate by bamboo plastic particles is placed in vulcanizing press, through precompressed, hot-forming, sizing of colding pressing.Bamboo powder content of the present invention up to 60%, raw material is inexpensive recyclable, the convenient and environmental protection of production process, polypropylene-base bamboo moulds that the cell morphology of foam composite material is good, density is low, specific tenacity is high, water-fast good heat resistance, has the good market space and application prospect.
Description
Technical field
The present invention relates to the preparation method that a kind of polypropylene-base bamboo moulds foam composite material, belong to Forestry Engineering field, also belong to field of compound material.
Background technology
Wood-plastic foam matrix material can overcome the defects such as wood plastic composite density is large, toughness is low, gives the performance of material uniqueness, has wide market outlook in fields such as building decoration, indoor decoration, artwork market, packed and transported, automotive upholsteries.Utilize the resource of bamboo wood, cost and performance advantage, its industrial wood waste filled thermoplastic is prepared bamboo-plastic composite material, not only greatly can improve the utilization ratio of bamboo wood, improve kind bamboo enthusiasm and the income level of bamboo agriculture, alleviate timber resources nervous; Also can strengthen the comprehensive utilization of waste plastic, reduce plastics " white " and pollute.Simultaneously, polypropylene (PP) is compared with polyethylene (PE) and polyvinyl chloride (PVC), there is excellent thermotolerance, chemical resistance, be easy to reclaim the advantages such as degraded, making processes environmental protection, therefore, polypropylene-base bamboo moulds the preparation of foam composite material and research has good economy, society and ecological benefits.At present, PP sill is moulded foam composite material and is still in the preliminary study stage, and the Wood-plastic foam goods that vegetable fibre content is high, Application Areas is wide, over-all properties is high need exploitation badly.
Polypropylene is crystalline polymer, before temperature reaches fusing point, flows hardly, once exceed melt temperature, viscosity sharply declines, and melt strength is low, is difficult to encase gas, bubble easily subsides or merges, and polypropylene expanded temperature range is narrow, and foaming process is difficult to control; In expanded polypropylene material, the melt viscosity adding membership raising matrix material in a large number of bamboo powder, affects the growth of complex, increases the foaming difficulty of matrix material further.At present mainly by methods such as blending and modifying, polymeric modification, reactive extrursion, cross-linking modified or direct use high melt strength, propylenes, improve the foam performance of PP.Wherein, cross-linking modified is by improving relative molecular mass, widening relative molecular mass distribution or introduce the method for long-chain branch on PP main chain, rheological property and the foam performance of PP can be improved, and the method cost of blending and modifying is lower, and nontoxic, environmental protection, but the composite property of preparation is often not high.Publication number is in the Chinese invention patent of CN200810024106, adopts the cross-linking modified injection-expansion molded technology providing a kind of polypropylene/wood powder/glass fiber compound material.Publication number is disclose a kind of micro-foaming polypropylene/bamboo powder composite material and preparation method thereof in the Chinese invention patent of CN102532720A.But above-mentioned two patents all adopt injection moulding to prepare foam composite material, the content of vegetable fibre (bamboo powder, wood powder) lower than 50%, and does not provide the foam composite material physical and mechanical property detected result of invention; And not adopting the crosslinked mode combined with blend modification technology, compression molding is prepared polypropylene-base bamboo and is moulded foam composite material.
Summary of the invention
The object of the invention is to there is in the actual use of polypropylene-base bamboo-plastic composite material the shortcoming that density is large, cost is high, restricted, the polypropylene expanded difficulty of poor toughness, Application Areas is large, adopt cross-linking modified and blending and modifying combined technology, provide a kind of polypropylene-base bamboo to mould the preparation method of foam composite material.The inexpensive easy recovery of raw material of the present invention, manufacture craft is simple, and process is environment friendly and pollution-free.
The present invention adopts following technical scheme to implement:
(1) torque rheometer forcing machine is utilized, by quality proportioning by polypropylene 30 parts, linking agent 0.5 ~ 5 part, additional crosslinker 0.5 ~ 5 part, whipping agent 1 ~ 6 part and blowing promotor 0.1 ~ 3 part, extrude obtained foaming concentrate, forcing machine three district temperature is all 160 ~ 170 DEG C, and rotor speed is 15 ~ 50r/min;
(2) bamboo powder was 105 DEG C of dryings 10 hours.By quality proportioning by polypropylene 70 parts, lubricant 0.5 ~ 4 part, antioxidant 0.6 ~ 4 part, anti UV agent 0.5 ~ 4 part, interfacial compatibilizer 3 ~ 15 parts and 50 ~ 140 parts, bamboo powder; (this intensification can be the heating mode of this area routine to put into high-speed mixer intensification successively; such as temperature programming) be uniformly mixed 10 ~ 15min; be warming up to 100 DEG C, make Preblend;
(3) Preblend that step (2) is obtained is placed on banburying in torque rheometer, with three sections of heating, three district's temperature are all 175 ~ 185 DEG C, and rotor speed is 20 ~ 60r/min, the banburying time is 12 ~ 16min, is ground into the bamboo plastic particles that particle diameter is 0.5 ~ 2mm after discharging through plastics strong crusher;
(4) foaming concentrate prepared by bamboo plastic particles step (3) prepared and step (1) mixes rear obtained foamed material; Foamed material is placed in vulcanizing press, moulds foam composite material through precompressed, hot-forming, the obtained polypropylene-base bamboo of sizing of colding pressing.Precompressed temperature is 175 ~ 180 DEG C, preload pressure 0 ~ 6MPa, squeeze time are every millimeter of thickness of slab 30 ~ 150s; Hot pressing temperature is 175 ~ 185 DEG C, hot pressing pressure 5 ~ 10MPa, and hot pressing time is every millimeter of thickness of slab 30 ~ 150s; Cold pressing pressure 0 ~ 6MPa, cold pressing, naturally cool to room temperature, form removal samples.
Above-mentioned steps (1) and the polypropylene described in (2) can adopt molecular weight, degree of crystallinity and the different two kinds of profax resin granular materials of melt index or powder, can be melt index be 0.5-15g/10min, weight-average molecular weight Mw be 100000 ~ 500000, degree of crystallinity be 30% ~ 80% profax resin granular material or powder; The water ratio of described bamboo powder is 1%-2%, and the particle diameter of bamboo powder is 40 ~ 200 orders; Described linking agent can be this area routine, and the present invention preferably 1,3(1,4)-bis-(tert-butylperoxyiso-propyl) benzene (BIPB); Described additional crosslinker can be this area routine, the preferred pentaerythritol triacrylate of the present invention (SR444) or cyanacrylate (TAIC) or Vinylstyrene (DVB); Described whipping agent can be this area routine, the preferred Cellmic C 121 of the present invention (AC); Described blowing promotor can be this area routine, one or more the combination in the preferred nano zine oxide of the present invention, stearic acid, calcium stearate, Zinic stearas; Described lubricant can be this area routine, one or more combination of preferred liquid paraffin of the present invention or stearic acid or stearate or epoxy soybean oil; Described antioxidant can be this area routine, the present invention's preferred hindered phenol anti-oxidants 1010/ phosphite antioxidant 168(and B225); Described anti UV agent can be this area routine, preferred UV770 or UV531 of the present invention; Described interfacial compatibilizer can be this area routine, the polypropylene of preferably acrylated compound class of the present invention grafting.
Feature of the present invention is: adopt the cross-linking modified technology combined with blending and modifying, overcome the problem of polypropylene difficulty foaming, compression molding develop bamboo powder content up to 60%, cell morphology is good, density is low, specific tenacity is high, water-fast heat-resisting chemical resistance is strong polypropylene-base bamboo moulds foam composite material; And raw material sources are extensive, preparation technology is simple, process environmental protection, goods degradable reclaim.This foam composite material has the good market space and development prospect, may be used on the fields such as material of construction, upholstery, artwork market, packed and transported, sports equipment, electrical apparatus insulation material and automotive upholstery.
Embodiment
The present invention is illustrated below in conjunction with embodiment, and following part is mass parts.PP in following embodiment
1for the acrylic plastering of melt index 3g/10min, degree of crystallinity 60%, weight-average molecular weight 354000, PP
2for the acrylic plastering of melt index 8g/10min, degree of crystallinity 45%, weight-average molecular weight 226000, whipping agent Cellmic C 121 is purchased from Shanghai Jie Yu Trade Co., Ltd., blowing promotor nano zine oxide (particle diameter is 40nm) is purchased from Hangzhou Wanjing New Material Co., Ltd., and (density is 1.36gcm to bamboo powder
-3particle diameter is 90-450 μm) purchased from jewel bamboo wood powder company limited of Zhejiang Linan City, antioxidant is that hindered phenol anti-oxidants 1010/ phosphite antioxidant 168 compound (B225) is purchased from Switzerland's vapour Bagong department, anti UV agent hindered amine light stabilizer (UV770) and Octabenzone (UV531) are all purchased from Switzerland's vapour Bagong department, and interfacial compatibilizer maleic anhydride inoculated polypropylene (MAPP) is purchased from Nanjing De Ba Chemical Co., Ltd..
Embodiment one
A kind of polypropylene-base bamboo of the present invention moulds the preparation method of foam composite material, comprises the following steps:
(1) in mass ratio by polypropylene PP
130 parts, linking agent 1,3(1,4)-bis-(tert-butylperoxyiso-propyl) benzene (BIPB) 2 parts, additional crosslinker cyanacrylate (TAIC) 1.5 parts, whipping agent Cellmic C 121 (AC) 1 part and blowing promotor are nano zine oxide and calcium stearate 0.08 part, mixture becoming of 1:1 proportioning in mass ratio, be placed in torque rheometer and extrude obtained foaming concentrate, forcing machine three district temperature is all 170 DEG C, and rotor speed is 20r/min;
(2) by bamboo powder at 105 DEG C dry 10 hours.By polypropylene PP
270 parts, 50 parts, bamboo powder, 1 part, lubricating fluid paraffin, antioxidant be hindered phenol anti-oxidants 1010/ phosphite antioxidant 168 compound (B225) 3 parts, anti UV agent hindered amine light stabilizer (UV770) 3 parts, interfacial compatibilizer maleic anhydride inoculated polypropylene (MAPP) 4 parts; mix with high-speed mixer, make Preblend; The Preblend of above-mentioned mixing is placed on banburying in torque rheometer, banburying three district temperature is all 180 DEG C, rotor speed is 40r/min, the banburying time is 12min, after discharging, be ground into through plastics strong crusher the bamboo plastic particles that particle diameter is 0.5-2mm;
(3) bamboo plastic particles and foaming concentrate are mixed obtained foamed material, foamed material is placed in vulcanizing press, mould foam composite material through precompressed, hot-forming, the obtained polypropylene-base bamboo being of a size of (200mm × 200mm × 4mm) of sizing of colding pressing.Precompressed temperature is 175 DEG C, preload pressure 2MPa, squeeze time 3min; Hot pressing temperature is 180 DEG C, hot pressing pressure 6MPa, and hot pressing time is 7min; Cold pressing pressure 2MPa, cold pressing, naturally cool to room temperature, then form removal takes out composite panel for test.
Embodiment two
Polypropylene-base bamboo moulds a preparation method for foam composite material, comprises the following steps:
(1) by quality proportioning by polypropylene PP
130 parts, linking agent 1,3(1,4)-bis-(tert-butylperoxyiso-propyl) benzene (BIPB) 1 part, additional crosslinker Vinylstyrene (DVB) 2 parts, whipping agent Cellmic C 121 (AC) 1.5 parts and the blowing promotor mixture of 1:1 (nano zine oxide and the Zinic stearas in mass ratio) 0.2 part, be placed in torque rheometer and extrude obtained foaming concentrate, forcing machine three district temperature is all 170 DEG C, and rotor speed is 30r/min;
(2) by bamboo powder at 105 DEG C dry 10 hours.By polypropylene PP
270 parts, 80 parts, bamboo powder, lubricant (stearic acid and calcium stearate are the mixture of 1:1 in mass ratio) 1 part, antioxidants hindered phenols class antioxidant 1010/phosphite antioxidant 168 compound (B225) 2 parts, anti UV agent (hindered amine light stabilizer UV770) 3 parts, interfacial compatibilizer maleic anhydride inoculated polypropylene (MAPP) 7 parts; mix with high-speed mixer, make Preblend; The Preblend of above-mentioned mixing is placed on banburying in torque rheometer, banburying three district temperature is all 180 DEG C, rotor speed is 35r/min, the banburying time is 13min, after discharging, be ground into through plastics strong crusher the bamboo plastic particles that particle diameter is 0.5-2mm;
(3) bamboo plastic particles and foaming concentrate are mixed, obtained foamed material, is placed in vulcanizing press by foamed material, moulds foam composite material through precompressed, hot-forming, the obtained polypropylene-base bamboo being of a size of (200mm × 200mm × 4mm) of sizing of colding pressing.Precompressed temperature is 175 DEG C, preload pressure 1.5MPa, squeeze time 4min; Hot pressing temperature is 180 DEG C, hot pressing pressure 6MPa, and hot pressing time is 7min; Cold pressing pressure 5MPa, cold pressing, naturally cool to room temperature, then form removal takes out composite panel for test.
Embodiment three
Polypropylene-base bamboo moulds a preparation method for foam composite material, comprises the following steps:
(1) by quality proportioning by polypropylene PP
130 parts, linking agent 1,3(1,4)-bis-(tert-butylperoxyiso-propyl) benzene (BIPB) 1 part, additional crosslinker pentaerythritol triacrylate (SR444) 3 parts, whipping agent Cellmic C 121 (AC) 2 parts and blowing promotor nano zine oxide 1 part, be placed in torque rheometer and extrude obtained foaming concentrate, forcing machine three district temperature is all 170 DEG C, and rotor speed is 25r/min;
(2) by bamboo powder at 105 DEG C dry 10 hours.By polypropylene PP
270 parts, 100 parts, bamboo powder, lubricant epoxy soybean oil 2.5 parts, antioxidants hindered phenols class antioxidant 1010/phosphite antioxidant 168 compound (B225) 2 parts, anti UV agent Octabenzone (UV531) 2 parts, interfacial compatibilizer maleic anhydride inoculated polypropylene (MAPP) 9 parts; mix with high-speed mixer, make Preblend; The Preblend of above-mentioned mixing is placed on banburying in torque rheometer, banburying three district temperature is all 180 DEG C, rotor speed is 35r/min, the banburying time is 13min, after discharging, be ground into through plastics strong crusher the bamboo plastic particles that particle diameter is 0.5-2mm;
(3) bamboo plastic particles and foaming concentrate are mixed, obtained foamed material, be placed on by foamed material in vulcanizing press, the polypropylene-base bamboo that must be of a size of (200mm × 200mm × 4mm) through precompressed, hot pressing, cold compaction moulds foam composite material.Precompressed temperature is 180 DEG C, preload pressure 2MPa, squeeze time 4min; Hot pressing temperature is 180 DEG C, hot pressing pressure 6MPa, and hot pressing time is 6min; Cold pressing pressure 2MPa, cold pressing, naturally cool to room temperature, then form removal takes out composite panel for test.
Embodiment four
Polypropylene-base bamboo moulds a preparation method for foam composite material, comprises the following steps:
(1) by quality proportioning by polypropylene PP
130 parts, linking agent 1,3(1,4)-bis-(tert-butylperoxyiso-propyl) benzene (BIPB) 1 part, additional crosslinker Vinylstyrene (DVB) 2.5 parts, whipping agent Cellmic C 121 (AC) 2.5 parts, the blowing promotor mixture of 1:2 (nano zine oxide and the Zinic stearas in mass ratio) 0.3 part, be placed in torque rheometer, its forcing machine part is utilized to obtain foaming concentrate, forcing machine three district temperature is all 170 DEG C, and rotor speed is 20r/min;
(2) by bamboo powder at 105 DEG C dry 10 hours.By polypropylene PP
270 parts, 120 parts, bamboo powder, lubricant stearic acid and whiteruss be 4 parts, mixture, antioxidants hindered phenols class antioxidant 1010/phosphite antioxidant 168 compound (B225) 1.5 parts, anti UV agent Octabenzone (UV531) 1.5 parts, the interfacial compatibilizer maleic anhydride inoculated polypropylene (MAPP) 11 parts of 1:1 in mass ratio; mix with high-speed mixer, make Preblend; The Preblend of above-mentioned mixing is placed on banburying in torque rheometer, banburying three district temperature is all 180 DEG C, rotor speed is 30r/min, the banburying time is 14min, after discharging, be ground into through plastics strong crusher the bamboo plastic particles that particle diameter is 0.5-2mm;
(3) bamboo plastic particles and foaming concentrate are mixed, obtained foamed material, be placed on by foamed material in vulcanizing press, the polypropylene-base bamboo that must be of a size of (200mm × 200mm × 4mm) through precompressed, hot pressing, cold compaction moulds foam composite material.Precompressed temperature is 180 DEG C, preload pressure 4MPa, squeeze time 3min; Hot pressing temperature is 180 DEG C, hot pressing pressure 6MPa, and hot pressing time is 8min; Cold pressing pressure 2MPa, colding pressing naturally cools to room temperature, then form removal take out composite panel for test.
The present embodiment polypropylene-base bamboo moulds foam composite material performance test methods:
By GB/T6343-2009 test density; Test three-point bending strength according to GB/T9341-2008, span 64cm, loading rate is 10mm/min; According to GB/T1040-2006 test tensile strength, rate of extension is 10mm/min; Notched Izod impact strength is tested according to GB/T1043-2008.According to above standard, shaping polypropylene-base bamboo is moulded foam composite material and be processed into corresponding test size, often organize experimental test 6 samples, average.
Below by way of detecting the effect proving the embodiment of the present invention 1, embodiment 2, embodiment 3 and embodiment 4, the performance test results that its polypropylene-base bamboo moulds foam composite material is as follows:
And corresponding non-expanded polypropylene based composites performance test results is as follows:
These results suggest that polypropylene-base bamboo of the present invention is moulded foam composite material and compares with common non-expanded polypropylene base bamboo-plastic composite material, density obviously declines, and specific tenacity obviously strengthens; Wherein, the density of matrix material reduces about 20%, although tensile strength and modulus in flexure decline slightly, flexural strength strengthens slightly, notched Izod impact strength significantly strengthens.
Claims (1)
1. polypropylene-base bamboo moulds a preparation method for foam composite material, comprises the following steps:
(1) by quality proportioning by polypropylene PP
130 parts, linking agent 1,3(1,4)-bis-(tert-butylperoxyiso-propyl) benzene 1 part, additional crosslinker Vinylstyrene 2.5 parts, whipping agent Cellmic C 121 2.5 parts, nano zine oxide and Zinic stearas in mass ratio 1:2 mixture form blowing promotor 0.3 part, be placed in torque rheometer, its forcing machine part is utilized to obtain foaming concentrate, forcing machine three district temperature is all 170 DEG C, and rotor speed is 20r/min; Described polypropylene PP
1for the acrylic plastering of melt index 3g/10min, degree of crystallinity 60%, weight-average molecular weight 354000;
(2) by bamboo powder at 105 DEG C dry 10 hours, by polypropylene PP
270 parts, 120 parts, bamboo powder, lubricant stearic acid and whiteruss be 4 parts, mixture, antioxidants hindered phenols class antioxidant 1010/phosphite antioxidant 168 compound 1.5 parts, anti UV agent Octabenzone 1.5 parts, the interfacial compatibilizer maleic anhydride inoculated polypropylene 11 parts of 1:1 in mass ratio; mix with high-speed mixer, make Preblend; The Preblend of above-mentioned mixing is placed on banburying in torque rheometer, banburying three district temperature is all 180 DEG C, rotor speed is 30r/min, the banburying time is 14min, after discharging, be ground into through plastics strong crusher the bamboo plastic particles that particle diameter is 0.5-2mm; Described polypropylene PP
2for the acrylic plastering of melt index 8g/10min, degree of crystallinity 45%, weight-average molecular weight 226000;
(3) bamboo plastic particles and foaming concentrate are mixed, obtained foamed material, is placed on foamed material in vulcanizing press, and the polypropylene-base bamboo that must be of a size of 200mm × 200mm × 4mm through precompressed, hot pressing, cold compaction moulds foam composite material; Precompressed temperature is 180 DEG C, preload pressure 4MPa, squeeze time 3min; Hot pressing temperature is 180 DEG C, hot pressing pressure 6MPa, and hot pressing time is 8min; Cold pressing pressure 2MPa, colding pressing naturally cools to room temperature, then
form removal samples.
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| CN103756146A (en) * | 2014-01-08 | 2014-04-30 | 沈阳化工大学 | Method for preparing foaming material from herbal fibers and plastic wastes |
| JP7303200B2 (en) | 2018-02-01 | 2023-07-04 | ダウ グローバル テクノロジーズ エルエルシー | Masterbatch with semi-crystalline polyolefin carrier resin |
| CN112352013A (en) * | 2018-02-01 | 2021-02-09 | 陶氏环球技术有限责任公司 | Masterbatch with semi-crystalline polyolefin carrier resin |
| CN108623907A (en) * | 2018-05-15 | 2018-10-09 | 温州市赢创新材料技术有限公司 | A kind of Sun-proof bamboo moulding material and preparation method thereof |
| CN112692947A (en) * | 2020-12-11 | 2021-04-23 | 宣城宏宇竹业有限公司 | Waterproof light bamboo material for biomass traffic guardrail and preparation method thereof |
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