CN1274759C - Weatherability type polyformaldehyde material and its preparation method - Google Patents
Weatherability type polyformaldehyde material and its preparation method Download PDFInfo
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- CN1274759C CN1274759C CN 200410040816 CN200410040816A CN1274759C CN 1274759 C CN1274759 C CN 1274759C CN 200410040816 CN200410040816 CN 200410040816 CN 200410040816 A CN200410040816 A CN 200410040816A CN 1274759 C CN1274759 C CN 1274759C
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Abstract
The present invention relates to a weatherproof type polyformaldehyde material and a preparation method thereof. The preparation method of the present invention is characterized in that the surface moist treatment of 0.05 to 5 parts by weight of liquid paraffin and 100 parts by weight of polyformaldehyde is carried out for 2 to 5 minutes; 0 to 10 parts by weight of inorganic particle, 0.01 to 5 parts by weight of light stabilizing agent and 0.01 to 5 parts by weight of thermal oxygen stabilizing agent are added, and the mixture is melted, mixed, extruded and granulated at the temperature of 140 to 220 DEG C to prepare the weatherproof type polyformaldehyde material. The weatherproof type polyformaldehyde material is molded in an injection mode at the temperature of 170 to 220 DEG C, and is prepared into a sample for an impacting, bending and tension test. After the manual weathering aging acceleration is carried out by the sample for 1200 hours by a xenon lamp weather test box, the impact strength conservation rate, the bending strength conservation rate, the tensile strength conservation rate and the breaking extension conservation rate of the sample respectively reach 84%, 104%, 103% and 61%, and are further higher than the corresponding performance conservation rates of unmodified polyformaldehyde. The ultraviolet light ageing resistance, hot oxygen aging resistance and hot water ageing resistance of the weatherproof type polyformaldehyde are superior to that of the unmodified polyformaldehyde.
Description
One, technical field
The present invention relates to a kind of weather resistant polyformaldehyde material and preparation method thereof, belong to polymer modification and manufacture field.
Two, background technology
The polyoxymethylene high comprehensive performance is one of five large-engineering plastics.But because constructional feature, Weatherability of Polyoxymethylene can be relatively poor, and its application is restricted.Improving the weathering resistance of polyoxymethylene, improve the ageing resistance of polyoxymethylene, is to promote the polyoxymethylene grade, widens the polyoxymethylene range of application, the important measures of development polyoxymethylene industry.At present relevant polyoxymethylene modified research is more, it mainly is tough-increased and reinforced modification, and it is less about the weather-proof study on the modification of polyoxymethylene, its relevant report relates generally to the modified system prescription, as Japanese Patent JP 06279651A2, world patent WO 9502012A1, Japanese Patent JP 11343383A2, Japanese Patent JP 11021416A2, Japanese Patent JP 09071715A2, world patent WO 9709383A1, Japanese Patent JP 94-105776, German patent DE 4442123A1, European patent EP 655482A2, German patent DE 4442167A1 etc. seldom relate to the more comprehensive mechanical property of modified system behind artificial accelerated weathering aging test certain hour and (comprise shock strength, flexural strength, tensile strength and elongation at break etc.) with aging before the comparison of mechanical property, not seeing has pair polyoxymethylene product to carry out artificial accelerated weathering aging test simultaneously, the ultraviolet light and aging test, thermo-oxidative ageing test and hot water weathering test.Shang Weijian has excellent in resistance weathering age performance, has the weather resistant polyoxymethylene product of good resistance to UV aging energy, heatproof air aging performance and heat-resisting water aging resistance to come out again.
Three, summary of the invention
The objective of the invention is provides a kind of weather resistant polyformaldehyde material and preparation method thereof at the deficiencies in the prior art, be characterized in polyoxymethylene, introducing inorganic particulate, photostabilizer and thermal oxidation stabilizer, by melting mixing, extrude, granulation, make the weather resistant polyformaldehyde material.
Purpose of the present invention is realized that by following measure wherein said raw material umber is parts by weight except that specified otherwise.
The recipe ingredient of weather resistant polyoxymethylene is:
100 parts of polyoxymethylene
0～10 part of inorganic particulate median size 30～100nm
0.01～5 part of photostabilizer
0.01～5 part of thermal oxidation stabilizer
0.05～5 part of whiteruss
Wherein inorganic particulate is any in zinc oxide, titanium dioxide, silicon-dioxide and the carbon black.
Photostabilizer is 2-hydroxyl-4-methoxy benzophenone, 2-hydroxyl-4-methoxyl group-4-chloro benzophenone, 2-hydroxyl-4-n-octyloxy-benzophenone, 2-(2 '-hydroxyl-3 ', 5 '-di-t-butyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-the 5-chlorinated benzotriazole, 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorinated benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-diamyl phenyl) benzotriazole, Succinic Acid and 4-hydroxyl-2,2,6, the polymer of 6-tetramethyl--1-piperidines alcohol, 4-benzoyloxy-2,2,6,6-tetramethyl piperidine or 2-(3,5-di-t-butyl-4-hydroxyl-benzene benzyl)-2-butyl 1,3-propanedioic acid two (1,2,2,6,6-pentamethyl--4-piperidyl) at least a in the ester.
Thermal oxidation stabilizer is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, 1,3,5-trimethylammonium-2,4,6-three-(4 '-hydroxyl-3 ', 5 '-di-t-butyl benzyl) benzene, 2, the 5-di-tert-butyl hydroquinone, hexylene glycol [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], N, N '-hexa-methylene two (3,5-two di-t-butyls-4-hydroxybenzene propionic acid amide), Tyox B, thio-2 acid two (14) ester, thio-2 acid two (18) ester, the thiodipropionate polyester, six hydrogen-1,3,5-three [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl-s-triazine or 2, at least a in 5-two-tertiary butyl-Resorcinol.
The preparation method of weather resistant polyformaldehyde material:
1, batching: 0.05～5 part of whiteruss and polyoxymethylene are added in the mixing equipment for 100 parts, mixed 2～5 minutes, make the polyoxymethylene solid surface wetting, add 0.1～5 part of 0～10 part of inorganic particulate, 0.1～5 part of photostabilizer and thermal oxidation stabilizer then, in mixed at room temperature 2～5 minutes.
2, the above-mentioned material that mixed is added in the twin screw extruder, in 140～220 ℃ of melting mixings of temperature, extrude, granulation, make the weather resistant polyoxymethylene.
3, injection moulding processing:, produce performance test samples such as stretching, bending, impact, thermal distortion, 170～220 ℃ of injection temperatures with the moulding on injection moulding machine of weather resistant polyformaldehyde material.
The performance test of weather resistant polyformaldehyde material:
1, weathering test:
A. artificial accelerated weathering aging test: weather resistant polyoxymethylene sample and unmodified polyoxymethylene sample are carried out artificial accelerated weathering aging test according to standard " GB/T16422.2-1999 idt ISO4892-2:1994 plastics laboratory light source exposure test method second section: xenon arc lamp ".Testing installation: ATLAS Ci4000 Xenon ArxWeather-Ometer.Test conditions: 65 ℃ ± 3 ℃ of blackboard temperatures, relative humidity (65 ± 5) %, the anhydrous time 102min ± 0.5min between the each water spraying time 18min ± 0.5min, twice water spray, wavelength region 290-2000nm, the spectral irradiance of 340nm is 0.5W/m
2Nm, the irradiance in 290～800nm wavelength region are 550W/m
2Test period: 1200 hours.
B. ultraviolet light and aging test: weather resistant polyoxymethylene sample and unmodified polyoxymethylene sample are placed homemade ultraviolet light and aging proofing box, continuous ageing 1000 hours, 40～50 ℃ of the temperature inside the box.
C. thermo-oxidative ageing: weather resistant polyoxymethylene sample and unmodified polyoxymethylene sample are placed 120 ℃ of convection oven, continuous ageing 1000 hours.
D. hot water is aging: weather resistant polyoxymethylene sample and unmodified polyoxymethylene sample are placed 90 ℃ of waters bath with thermostatic control, continuous ageing 1000 hours.
2, Mechanics Performance Testing
A. impact property test:, measure the notched Izod impact strength of sample with XJ-40 type shock-testing machine according to ISO 179-1993 (E) standard.23 ℃ of probe temperatures, testing method are the simply supported beam ballistic method.
B. bending property test: the sample flexural strength is measured with 4302 type INSTRON universal testing machines.23 ℃ of probe temperatures.
C. tensile property test:, measure the tensile strength and the elongation at break of sample with 4302 type INSTRON universal testing machines according to ISO 527/1-1993 (E) standard.23 ℃ of probe temperatures, rate of extension 50mm/min.
The present invention has following advantage:
1. the performance test data of weather resistant polyoxymethylene behind artificial accelerated weathering aging, ultraviolet light and aging, thermo-oxidative ageing and hot water solarization shows that its weather-resistant performance, resistance to UV aging energy, heatproof air aging performance and heat-resisting water aging resistance all are better than unmodified polyoxymethylene.Test data is seen Fig. 1, Fig. 2, Fig. 3 and Fig. 4.
2. the manufacture method of weather resistant polyoxymethylene is simple, and raw material is easy to obtain, and equipment used is a conventional equipment, is easy to suitability for industrialized production.
Four, description of drawings
Fig. 1 is weather resistant polyoxymethylene and the unmodified polyoxymethylene comparison diagram through the conservation rate of artificial shock strength, tensile strength and the elongation at break of accelerated weathering aging after 1200 hours.Among the figure
Be shock strength, tensile strength and the elongation at break conservation rate of unmodified polyoxymethylene,
Shock strength, tensile strength and elongation at break conservation rate for the weather resistant polyoxymethylene.The result shows: through artificial accelerated weathering aging after 1200 hours.The shock strength of weather resistant polyoxymethylene, tensile strength and elongation at break conservation rate are significantly higher than shock strength, tensile strength and the elongation at break conservation rate of unmodified polyformaldehyde material, and the former weather-resistant performance is better than the latter.
Fig. 2 is weather resistant polyoxymethylene and the unmodified polyoxymethylene comparison diagram through the conservation rate of shock strength, tensile strength and the elongation at break of ultraviolet light and aging after 1000 hours.Among the figure
Be shock strength, tensile strength and the elongation at break conservation rate of unmodified polyoxymethylene,
Shock strength, tensile strength and elongation at break conservation rate for the weather resistant polyoxymethylene.The result shows: through ultraviolet light and aging after 1000 hours.The shock strength of weather resistant polyoxymethylene, tensile strength and elongation at break conservation rate are significantly higher than shock strength, tensile strength and the elongation at break conservation rate of unmodified polyoxymethylene, and the former resistance to UV aging can be better than the latter.
Fig. 3 is weather resistant polyoxymethylene and the unmodified polyoxymethylene comparison diagram through the conservation rate of shock strength, tensile strength and the elongation at break of 120 ℃ of thermo-oxidative ageings after 1000 hours.Among the figure
Be shock strength, tensile strength and the elongation at break conservation rate of unmodified polyoxymethylene,
Shock strength, tensile strength and elongation at break conservation rate for the weather resistant polyoxymethylene.The result shows: through 120 ℃ of thermo-oxidative ageings after 1000 hours.The shock strength of weather resistant polyoxymethylene and elongation at break conservation rate are significantly higher than the shock strength and the elongation at break conservation rate of unmodified polyoxymethylene, and the stretching strength retentivity difference is little, and the former heatproof air aging performance is better than the latter.
Fig. 4 is the comparison diagram of the conservation rate of weather resistant polyoxymethylene and shock strength, tensile strength and the elongation at break of unmodified polyoxymethylene after 90 ℃ of hot water wore out 1000 hours.Among the figure
Be shock strength, tensile strength and the elongation at break conservation rate of unmodified polyoxymethylene,
Shock strength, tensile strength and elongation at break conservation rate for the weather resistant polyoxymethylene.The result shows: after 90 ℃ of hot water wore out 1000 hours.The shock strength of weather resistant polyoxymethylene and elongation at break conservation rate are higher than the shock strength and the elongation at break conservation rate of unmodified polyoxymethylene, and the stretching strength retentivity difference is little, and the former heat-resisting water aging resistance is better than the latter.
Five, embodiment
Below by embodiment the present invention is specifically described, be necessary to be pointed out that at this present embodiment only is used for the present invention is further specified, can not be interpreted as limiting the scope of the invention.The person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of the invention described above.
Embodiment 1
Polyoxymethylene 1000g is added whiteruss 10 grams; mix; add four [β-(3 then; the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 3g; Tyox B 1.5g; 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazole 0.5g, Succinic Acid and 4-hydroxyl-2; 2; 6,6-tetramethyl--1-piperidines alcohol polymer 0.5g fully mixes; place twin screw extruder then; extrude in 140～220 ℃ of melt blendings of temperature,, make the weather resistant polyformaldehyde material again through the dicing machine pelletizing; in 170～190 ℃ of injection mouldings of temperature.
Embodiment 2
Polyoxymethylene 1000g is added whiteruss 10 grams; mix; add nano zine oxide 30g then; four [β-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 3g, Tyox B 1.5g, 2-(2 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazole 0.5g; Succinic Acid and 4-hydroxyl-2,2,6; the polymer 0.5g of 6-tetramethyl--1-piperidines alcohol; fully mix, place twin screw extruder then, extrude in 150～210 ℃ of melt blendings of temperature; through the dicing machine pelletizing, make the weather resistant polyformaldehyde material again; in 170～200 ℃ of injection mouldings of temperature.
Embodiment 3
Polyoxymethylene 1000g is added whiteruss 20 grams; mix; add four [β-(3 then; the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 3g; Tyox B 1.5g; 2-(2 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazole 0.5g; fully mix; place twin screw extruder then, extrude in 140～210 ℃ of melt blendings of temperature, again through the dicing machine pelletizing; make the weather resistant polyformaldehyde material, in 170～200 ℃ of injection mouldings of temperature.
Embodiment 4
Polyoxymethylene 1000g is added whiteruss 5 grams; mix; add carbon black 15g then; four [β-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 3g, Tyox B 15g, 2-(2 '-hydroxyl-3 '; 5 '-di-tert-butyl-phenyl)-5-chlorinated benzotriazole 0.5g; Succinic Acid and 4-hydroxyl-2,2,6; the polymer 0.5g of 6-tetramethyl--1-piperidines alcohol; fully mix, place twin screw extruder then, extrude in 150～220 ℃ of melt blendings of temperature; through the dicing machine pelletizing, make the weather resistant polyformaldehyde material again; in 170～220 ℃ of injection mouldings of temperature.
Embodiment 5
Polyoxymethylene 1000g is added whiteruss 5 grams; mix; add nano titanium oxide 20g then; four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 3g, hexylene glycol [β-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic ester 3g; 2-(2 '-hydroxyl-3 ', 5 '-di-t-butyl) benzotriazole 0.5g, Succinic Acid and 4-hydroxyl-2; 2; 6, the polymer 0.5g of 6-tetramethyl--1-piperidines alcohol fully mixes; place twin screw extruder then; extrude in 140～200 ℃ of melt blendings of temperature,, make the weather resistant polyformaldehyde material again through the dicing machine pelletizing; in 170～200 ℃ of injection mouldings of temperature.
Embodiment 6
Polyoxymethylene 1000g is added an amount of paraffin 5 grams; mix, add silica 1 0g then, four [β-(3; the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 3g; thiodipropionate polyester 15g, 2-hydroxyl-4-methoxy benzophenone 0.5g, Succinic Acid and 4-hydroxyl-2; 2; 6, the polymer 0.5g of 6-tetramethyl--1-piperidines alcohol, 4-benzoyloxy-2; 2; 6,6-tetramethyl piperidine 0.1g fully mixes; place twin screw extruder then; extrude in 150～220 ℃ of melt blendings of temperature,, make the weather resistant polyformaldehyde material again through the dicing machine pelletizing; in 170～190 ℃ of injection mouldings of temperature.
Embodiment 7
Polyoxymethylene 1000g is added whiteruss 5 grams; mix; add tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester 3g then, thio-2 acid two (18) ester 15g; 2-hydroxyl-4-methoxy benzophenone 0.5g; fully mix, place twin screw extruder then, extrude in 150～210 ℃ of melt blendings of temperature; again through the dicing machine pelletizing, make the weather resistant polyformaldehyde material, in 170～200 ℃ of injection mouldings of temperature.
Embodiment 8
Polyoxymethylene 1000g is added whiteruss 5 grams; mix; add 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorinated benzotriazole 0.1g then; tricresyl phosphite (2; the 4-di-tert-butyl-phenyl) ester 3g; thio-2 acid two (14) ester 15g; 2-hydroxyl-4-n-octyloxy-benzophenone 0.5g; fully mix; place twin screw extruder then; extrude in 140～200 ℃ of melt blendings of temperature, again through the dicing machine pelletizing, make the weather resistant polyformaldehyde material, in 170～210 ℃ of injection mouldings of temperature.
Embodiment 9
Polyoxymethylene 1000g is added whiteruss 5 grams; mix; add 1 then; 3,5-trimethylammonium-2,4; 6-three-(4 '-hydroxyl-3 '; 5 '-di-t-butyl benzyl) benzene 0.1g, six hydrogen-1,3; 5-three [β-(3; the 5-di-tert-butyl-hydroxy phenyl) propionyl-s-triazine 3g, 2,5-two-tertiary butyl-Resorcinol 15g; 2-(2 '-hydroxyl-3 '; 5 '-diamyl phenyl) benzotriazole 0.5g, 2-hydroxyl-4-methoxyl group-4-chloro benzophenone 0.1g fully mixes; place twin screw extruder then; extrude in 150～220 ℃ of melt blendings of temperature,, make the weather resistant polyformaldehyde material again through the dicing machine pelletizing; in 170～210 ℃ of injection mouldings of temperature.
Claims (4)
1, a kind of weather resistant polyformaldehyde material is characterized in that the recipe ingredient of this weather resistant polyformaldehyde material is by weight:
100 parts of polyoxymethylene
0～10 part of inorganic particulate median size 30～100nm
0.01～5 part of photostabilizer
0.01～5 part of thermal oxidation stabilizer
0.05～5 part of whiteruss
Wherein inorganic particulate is any in zinc oxide, titanium dioxide, silicon-dioxide and the carbon black, this weather resistant polyformaldehyde material was through the artificial accelerated weathering aging of xenon arc type climatic test chamber 1200 hours, and sample shock strength conservation rate, flexural strength conservation rate, stretching strength retentivity and elongation at break conservation rate reach 84%, 104%, 103% and 61% respectively.
2, modified, weather resisting type polyformaldehyde material according to claim 1, it is characterized in that photostabilizer is 2-hydroxyl-4-methoxy benzophenone, 2-hydroxyl-4-methoxyl group-4-chloro benzophenone, 2-hydroxyl-4-n-octyloxy-benzophenone, 2-(2 '-hydroxyl-3 ', 5 '-di-t-butyl) benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-the 5-chlorinated benzotriazole, 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorinated benzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-diamyl phenyl) benzotriazole, Succinic Acid and 4-hydroxyl-2,2,6, the polymer of 6-tetramethyl--1-piperidines alcohol, 4-benzoyloxy-2,2,6,6-tetramethyl piperidine or 2-(3,5-di-t-butyl-4-hydroxyl-benzene benzyl)-2-butyl 1,3-propanedioic acid two (1,2,2,6,6-pentamethyl--4-piperidyl) at least a in the ester.
3, modified, weather resisting type polyformaldehyde material according to claim 1, it is characterized in that thermal oxidation stabilizer is four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, 1,3,5-trimethylammonium-2,4,6-three-(4 '-hydroxyl-3 ', 5 '-di-t-butyl benzyl) benzene, 2,5 di tert butyl hydroquinone, hexylene glycol [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester], N, N '-hexa-methylene two (3,5-di-t-butyl-4-hydroxybenzene propionic acid amide), Tyox B, thio-2 acid two (14) ester, thio-2 acid two (18) ester, the thiodipropionate polyester, six hydrogen-1,3,5-three [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl-s-triazine or 2, at least a in 5-two-tertiary butyl-Resorcinol.
4, as the preparation method of modified, weather resisting type polyformaldehyde material as described in the claim 1～3, it is characterized in that:
With whiteruss 0.05～5 weight part, polyoxymethylene 100 weight parts add in the mixing machine, under room temperature, mixed 2～5 minutes, then with inorganic particulate 0～10 weight part, photostabilizer 0.1～5 weight part, thermal oxidation stabilizer 0.1～5 weight part, add in the twin screw extruder, in 140～220 ℃ of melting mixings of temperature, extrude, granulation, make the weather resistant polyformaldehyde material, the injection moulding processing temperature is 170～220 ℃.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US7396492B2 (en) * | 2006-03-30 | 2008-07-08 | Kenneth Leon Price | Electrically conductive resin compounds based on polyoxymethylene and highly structured carbon black |
| CN102675818B (en) * | 2012-05-24 | 2015-01-28 | 兖矿鲁南化肥厂 | Reinforced and toughened polyformaldehyde and preparation method thereof |
| CN102719053B (en) * | 2012-05-25 | 2013-11-06 | 广州市景龙装饰工程有限公司 | Shady safety helmet and preparation method thereof |
| CN103059500B (en) * | 2013-01-05 | 2015-04-15 | 上海瀚氏模具成型有限公司 | Anti-illumination aging polyformaldehyde plastic for car interior parts and preparation method thereof |
| CN103992614A (en) * | 2014-06-09 | 2014-08-20 | 云南云天化股份有限公司 | Polyacetal resin composition and preparation method thereof |
| CN109206834A (en) * | 2017-07-04 | 2019-01-15 | 镇江市睿泽文化传播有限公司 | A kind of acetal plastic with photostability |
| CN117430538A (en) * | 2018-05-24 | 2024-01-23 | 川斯勒佰尔公司 | Thioester cationic lipids |
| CN112391028A (en) * | 2020-11-16 | 2021-02-23 | 南京中创智元科技有限公司 | Preparation method of high-temperature-resistant anti-ultraviolet polyformaldehyde engineering plastic |
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