CN1128173C - Transparent nucleator for polypropylene and its preparing process and usage - Google Patents
Transparent nucleator for polypropylene and its preparing process and usage Download PDFInfo
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- CN1128173C CN1128173C CN 99122080 CN99122080A CN1128173C CN 1128173 C CN1128173 C CN 1128173C CN 99122080 CN99122080 CN 99122080 CN 99122080 A CN99122080 A CN 99122080A CN 1128173 C CN1128173 C CN 1128173C
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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Abstract
The present invention relates to a polypropylene nucleating transparent agent which is a mixture composed of dehydroabietic acid and dehydroabietic acid metal salt according to the proportion of 40 to 90: 10 to 60. The making method of the polypropylene nucleating transparent agent comprises the steps that 40 to 90 portions of the dehydroabietic acid and 10 to 60 portions of the dehydroabietic acid metal salt are mixed, ground and sieved to make into the polypropylene nucleating transparent agent; the polypropylene nucleating transparent agent of the present invention can be used as a nucleating agent of homo-polypropylene, random copolymerized polypropylene and block copolymerized polypropylene. The nucleating agent improves the transparency of polypropylene plastics and enhances the crystallization temperature, the tensile strength and the heat deformation temperature of polypropylene.
Description
The present invention relates to a kind of preparation method of transparent nucleator for polypropylene, particularly a kind of nilox resin that adopts is the preparation method of feedstock production transparent nucleator for polypropylene.
Polypropylene is a class excellent property, low price, of many uses, translucent crystalline plastics, can improve the polyacrylic transparency by adding nucleator, obtains the transparent polypropylene plastics.The transparent nucleator for polypropylene of Xiao Shouing mainly contains sorbyl alcohol type and organophosphate two big classes in the market.The nineties, Japanese dimerization company (Japan Polychem Cerporation) adopts the metal-salt of the various resinous acids of rosin (comprise and adopt dehydroabietic acid) to make nucleator, improves the transparency (EP.785,231) of acrylic plastering.But Gum Rosin acid metal salt fusing point is higher, bad dispersibility in polypropylene.New Japanese chemical company (New JapanChemical Co.Ltd.) is a starting raw material with the dehydroabietic acid, make the molecular crystal of each acid and salt, obtain polyacrylic transparent nucleator (WO9806784), this patent emphasizes that the advantage of molecular crystal is to obtain than the low-melting same hydrochlorate xln of salt, good dispersity in acrylic resin, but preparation molecular crystal complex process, the product loss is big.
The objective of the invention is to overcome the bad dispersibility of simple Gum Rosin hydrochlorate in polypropylene, improve the shortcoming of polypropylene transparent DeGrain, and preparation acid, molecules of salt crystallization processes complexity, shortcoming that productive rate is low, and propose directly to adopt disproportionation rosin as starting raw material, by the preparation ethanolamine salt, in nilox resin, extract dehydroabietic acid, make dehydrogenated metallic abietate then, with simple acid, the composite method of salt, make polypropylene nucleater.
Rosin based transparent nucleator for polypropylene of the present invention is the mixture with following structural formula dehydroabietic acid and dehydrogenated metallic abietate thereof, wherein dehydroabietic acid accounts for 40-90 part (weight part), be preferably 60～70 parts, dehydrogenated metallic abietate accounts for 10-60 part (weight part), is preferably 30～40 parts.
Dehydroabietic acid:
Dehydrogenated metallic abietate:
Or
M
1Be Li, Na, K basic metal, M
2Be Ca, Mg alkaline-earth metal.
Rosin based transparent nucleator for polypropylene of the present invention is that to adopt nilox resin, thanomin, Glacial acetic acid, hydrochloric acid, alkali metal hydroxide, alkaline earth metal oxide, anhydrous diethyl ether, second alcohol and water be raw material, and its method for making is carried out in the following order step by step:
1. building-up reactions:
(1) preparation dehydroabietic acid ethanolamine salt:
In reactor, add 100 parts of (weight part) nilox resins and 100～300 parts of anhydrous diethyl ethers, add 10～40 parts of thanomins, stirred 0.5～10 minute, and separated out white precipitate, filtration under diminished pressure, use solvent wash, refilter twice, vacuum-drying gets dehydroabietic acid ethanolamine salt crude product, twice purifying of recrystallization in ethanol gets the dehydroabietic acid ethanolamine salt.
(2) preparation dehydroabietic acid:
In reactor, add 100 parts of above-mentioned dehydroabietic acid ethanolamine salts and 100～500 parts of Glacial acetic acid, heating for dissolving adds 20～100 parts of water or dense HCl, stirs and cooling gradually, separate out white precipitate, filtration under diminished pressure, and with Glacial acetic acid and water mixed liquid washing, refilter, vacuum-drying, get the dehydroabietic acid crude product, twice purifying of recrystallization in ethanol gets dehydroabietic acid.
(3) preparation dehydrogenated metallic abietate:
In reactor, add 100 parts of above-mentioned dehydroabietic acids and 100～500 parts of dehydrated alcohols, heating for dissolving, 10～40 parts of alkali metal hydroxides or the alkaline earth metal oxide that will be dissolved in dehydrated alcohol again add reactor, 20～100 ℃ of reactions 0.1～2 hour, remove partial solvent through underpressure distillation, filter, obtain dehydrogenated metallic abietate.
Above-mentioned alkali metal hydroxide is Li (OH), KOH, NaOH.Above-mentioned alkaline earth metal oxide is CaO, MgO..
2. composite transparent nucleator for polypropylene:
40～90 parts of above-mentioned dehydroabietic acids and 10～60 parts of above-mentioned dehydrogenated metallic abietates are mixed, and through grinding, sieving, getting particle diameter is the rosin based transparent nucleator for polypropylene of 40～150 μ m.
The structure of aforesaid method synthetic dehydroabietic acid and dehydrogenated metallic abietate is identified by fusing point, acid number, UV spectrum, infrared spectra and gas-chromatography.The various eigenwerts of gained compound come together in table 1.
Table 1 dehydroabietic acid and dehydrogenated metallic abietate eigenwert
| Compound | Fusing point ℃ | Acid number mgKOH/g | UV spectrum EtOH λ max(nm) | Infrared spectra | Gas-chromatography |
| Dehydroabietic acid | 172-173 | 186.9 | 268，276 | 1695cm -1(V C＝O) 1280cm -1(V C-O) 950cm -1(δ O-H) | Unimodal |
| Dehydroabietic acid sylvite | 300-305 | 0.0 | 265，273 | 1547cm -1(V (a)COO -) 1390cm -1(V (s)COO -) | / |
| The dehydroabietic acid sodium salt | 300-305 | 0.0 | 265，273 | 1547cm -1(V (a)COO -) 1390cm -1(V (s)COO -) | / |
The purposes of the rosin based transparent nucleator for polypropylene of the present invention's preparation is as homo-polypropylene, and the nucleator of atactic copolymerized polypropene, block copolymerization polypropylene pellet or powder, nucleator consumption are 0.5～10 ‰, and wherein 2～5 ‰ is better.It is abundant, cheap that this nucleator has raw material sources, advantages such as synthesis technique is simple, production cost is low, easy homodisperse, and the kind of ratio that can be by adjusting dehydroabietic acid and dehydrogenated metallic abietate and adjustment dehydrogenated metallic abietate is re-dubbed different compositions easily and satisfies the transparent nucleator for polypropylene of different requirements.The rosin based polypropylene nucleater of the present invention's preparation is uniformly dispersed in polypropylene, does not find not dispersive nucleator particle in the material bar that melt extrudes.This nucleator has not only improved the transparency of acrylic plastering, and has improved the crystalling propylene temperature, has shortened shaping cycle, has improved the tensile strength of acrylic plastering, and heat-drawn wire is a kind of good transparent nucleator for polypropylene.
Embodiment 1
In reactor, add 200 parts of nilox resins and 400 parts of anhydrous diethyl ethers, stirring and dissolving, and be chilled to 0 ℃ with ice bath, slowly add 40 parts of thanomins, behind the stir about 30 seconds, separate out white precipitate, filtration under diminished pressure is with twice of 80 parts of anhydrous diethyl ether drip washing, vacuum drying, get 192 parts of dehydroabietic acid ethanolamine salt crude products, recrystallization twice in ethanol, gets 115.5 parts of dehydroabietic acid ethanolamine salts.
100 parts of above-mentioned dehydroabietic acid ethanolamine salts and 300 parts of Glacial acetic acid add reactor, the heated and stirred dissolving adds 80 parts of distilled water, stirs and cooling gradually, separate out white precipitate after 10 minutes, be cooled to 0 ℃, filtration under diminished pressure is with twice of 80 parts of Glacial acetic acid, 20 parts of water mixed liquid drip washing, in 80 ℃ of following vacuum-dryings 3 hours, get 80 parts of dehydroabietic acid crude products, recrystallization twice in ethanol, gets 50.5 parts of dehydroabietic acids.
Dehydroabietic acid behind 20 parts of purifying and 50 parts of dehydrated alcohols add reactors, the heated and stirred dissolving, 4.56 a part KOH (purity 〉=82%) is dissolved in 50 parts of dehydrated alcohols, add reactor, react half an hour down in 60 ℃, underpressure distillation removes and desolvates, and 60 ℃ of vacuum were dried by the fire 2 hours, got 17.7 parts of dehydroabietic acid sylvite.
14 parts of above-mentioned dehydroabietic acids and above-mentioned dehydroabietic acid sylvite mix for 6 parts, grind and sieve, transparent nucleator for polypropylene 1, particle diameter is 65 μ m.
10 parts of above-mentioned dehydroabietic acids and above-mentioned dehydroabietic acid sylvite mix for 10 parts, grind and sieve, transparent nucleator for polypropylene 2, particle diameter is 65 μ m.
Embodiment 2
In reactor, add 200 parts of nilox resins and 400 parts of anhydrous diethyl ethers, stirring and dissolving, slowly add 40.0 parts of thanomins, stir and separate out white precipitate after 30 seconds, filtration under diminished pressure is with twice of 100 parts of anhydrous diethyl ether drip washing, vacuum drying, 174.5 parts of dehydroabietic acid ethanolamine salt crude products exist, recrystallization twice in ethanol, 105.2 parts of dehydroabietic acid ethanolamine salts.
100 parts of above-mentioned dehydroabietic acid ethanolamine salts and 300 parts of Glacial acetic acid join reactor, the heated and stirred dissolving, add 80 parts of concentrated hydrochloric acids (weight percent 36～38%), stir also and be cooled to 0 ℃ gradually, separate out white precipitate, filtration under diminished pressure after tens minutes, with twice of 80 parts of Glacial acetic acid, the drip washing of 20 parts of concentrated hydrochloric acid mixing acid, in 80 ℃ of following vacuum-dryings 3 hours, get 85.5 parts of dehydroabietic acid crude products, twice purifying of recrystallization gets 54.0 parts of dehydroabietic acids in ethanol.
Dehydroabietic acid and 50 parts of dehydrated alcohols behind 20 parts of above-mentioned purifying join in the reactor, the heated and stirred dissolving, 2.80 add reactor after a part NaOH (purity 〉=96%) is dissolved in 50 parts of dehydrated alcohols, stir about half a minute, separate out precipitation, be cooled to 0 ℃, filtration under diminished pressure, with 10 parts of dehydrated alcohol drip washing twice,, get 16.5 parts of dehydroabietic acid sodium salts in 60 ℃ of following vacuum-dryings 2 hours.
14 parts of above-mentioned dehydroabietic acids and 6 parts of above-mentioned dehydroabietic acid sodium salts mix, grind and sieve, transparent nucleator for polypropylene 3, particle diameter is 125 μ m.
10 parts of above-mentioned dehydroabietic acids and 10 parts of above-mentioned dehydroabietic acid sodium salts mix, grind and sieve, transparent nucleator for polypropylene 4, particle diameter is 125 μ m.
Embodiment 3
100 parts of polypropylene (melting index 6.0g/10min), 1,0.1 part of calcium stearate of transparent nucleator for polypropylene of 0.5 part of embodiment 1 preparation, 0.1 part of oxidation inhibitor blend extruding pelletization in screw extrusion press is made sample after the blend pellet drying on injector.Sample yield strength 38.0MPa, 119.6 ℃ of Tcs, 0.8mm thick coupons 500,600,700,800nm place transmittance is respectively: 41.9%47.5% and 54.7% 36.0%,, above-mentioned each value of virgin pp is respectively 36.2MPa, 112.2 ℃, 21.6%, 24.9%, 29.0% and 35.8%.Embodiment 4
100 parts of polypropylene (melting index 6.0g/10mm), 2,0.1 parts of calcium stearates of transparent nucleator for polypropylene of 0.5 part of embodiment 1 preparation, 0.1 part of oxidation inhibitor blend in screw extrusion press is extruded, and granulation is made sample after the blend pellet drying on injector.Sample yield strength 39.7MPa, 122.4 ℃ of Tcs, 0.8mm thick coupons 500,600,700,800nm place transmittance is respectively: 28.4%, 33.2%, 38.6% and 45.0%, above-mentioned each value of virgin pp is respectively 36.2MPa, 112.2 ℃, 21.6%, 24.9%, 29.0% and 35.8%.
Embodiment 5
0.5 the transparent nucleator for polypropylene 3 of part embodiment 2 preparations, 0.1 part calcium stearate, 0.1 part oxidation inhibitor, be dissolved in 5 part of 95% ethanol, mix with 100 parts of polypropylene (melting index 6.0g/10min), the blend in screw extrusion press of dry back is extruded, granulation, on injector, make sample after the blend pellet drying, its yield strength is 37.6MPa, Tc is 119.7 ℃, 0.8mm thick coupons is 500,600,700,800nm place transmittance is respectively 32.0%, 38.6%, 43.9%, 50.9%, and virgin pp is respectively 36.2MPa, 112.2 ℃, 21.6%, 24.9%, 29.0% and 35.8%.
Embodiment 6
0.5 the transparent nucleator for polypropylene 4 of part embodiment 2 preparations, 0.1 part calcium stearate, 0.1 part oxidation inhibitor is dissolved in 5 part of 95% ethanol, mix with 100 parts of polypropylene (melting index 6.0g/10min), the blend in screw extrusion press of dry back is extruded, granulation, on injector, make sample after the blend pellet drying, its yield strength is 38.1MPa, Tc is 120.7 ℃, 0.8mm thick coupons is 500,600,700,800nm place transmittance is respectively 32.2%, 37.4%, 43.0% and 50.5%, and virgin pp is respectively 36.2MPa, 112.2 ℃, 21.6%, 24.9%, 29.0% and 35.8%
Embodiment 7
100 parts of polypropylene (melting index 7.0g/10min), 0.3 the transparent nucleator for polypropylene 1 of part embodiment 1 preparation, 0.1 part calcium stearate, 0.1 part oxidation inhibitor blend in screw extrusion press is extruded, granulation, after the blend pellet drying, on injector, make sample, its yield strength is 37.8MPa, crystallization intensity is 119.2 ℃, 0.8mm thick sample gas is 500,600,700,800nm place transmittance is respectively 29.0%, 35.0%, 41.1% and 47.5%, and above-mentioned each value of virgin pp is respectively 35.8MPa, 112.4 ℃, 23.4%, 25.7%, 29.0% and 35.8%.
Embodiment 8
0.3 the transparent nucleator for polypropylene 3 of part embodiment 2 preparations, 0.1 part calcium stearate, 0.1 part oxidation inhibitor, be dissolved in 5 part of 95% ethanol, mix with 100 parts of polypropylene (melting index 7.0g/10min), the blend in screw extrusion press of dry back is extruded, granulation, on injector, make sample after the blend pellet drying, its yield strength is 37.8MPa, Tc is 119.5 ℃, and the thick coupons of 0.8mm is 500,600,700,800nm place transmittance is respectively 28.2%, 33.0%, 37.5% and 45.4%, and virgin pp is respectively 35.8MPa, 112.4 ℃, 23.4%, 25.7%, 29.0% and 35.8%.
Claims (3)
1. the preparation method of a transparent nucleator for polypropylene is characterized in that carrying out step by step in the following order:
(1) building-up reactions:
1. prepare the dehydroabietic acid ethanolamine salt:
In reactor, add 100 parts of (weight part) nilox resins and 100～300 parts of anhydrous diethyl ethers, adds 10～40 parts of thanomins, stirred 0.5～10 minute, separate out white precipitate, after filtration, washing, purifying, must the dehydroabietic acid ethanolamine salt,
2. prepare dehydroabietic acid:
Add 100 parts of above-mentioned dehydroabietic acid ethanolamine salts and 100～500 parts of Glacial acetic acid in reactor, heating for dissolving adds 20～100 parts of water or dense HCl, stirs and cooling gradually, separates out white precipitate, after filtration, washing, purifying, gets dehydroabietic acid,
3. prepare dehydrogenated metallic abietate:
In reactor, add 100 parts of above-mentioned dehydroabietic acids and 100～500 parts of dehydrated alcohols, heating for dissolving, 10～40 parts of alkali metal hydroxides or the alkaline earth metal oxide that will be dissolved in dehydrated alcohol again added reactor, 20～100 ℃ of reactions 0.1～2 hour, obtain dehydrogenated metallic abietate
(2) composite transparent nucleator for polypropylene:
40～90 parts of above-mentioned dehydroabietic acids and 10～60 parts of above-mentioned dehydrogenated metallic abietates are mixed, and through grinding, sieving, getting particle diameter is the transparent nucleator for polypropylene of 40～150 μ m,
Above-mentioned each material by weight.
2. the preparation method of a kind of transparent nucleator for polypropylene according to claim 1 is characterized in that described alkali metal hydroxide is LiOH, KOH or NaOH.
3. the preparation method of a kind of transparent nucleator for polypropylene according to claim 1 is characterized in that described alkaline earth metal oxide is CaO or MgO.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99122080 CN1128173C (en) | 1999-10-28 | 1999-10-28 | Transparent nucleator for polypropylene and its preparing process and usage |
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| CN 99122080 CN1128173C (en) | 1999-10-28 | 1999-10-28 | Transparent nucleator for polypropylene and its preparing process and usage |
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| CN1128173C true CN1128173C (en) | 2003-11-19 |
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| CN103450619B (en) * | 2013-08-27 | 2015-06-10 | 陕西省轻工业研究设计院 | Method for preparing heat-resisting anti-impact HTPP (High Transparent Polypropylene) through T30S modification |
| CN106279766A (en) * | 2016-08-29 | 2017-01-04 | 浙江比例包装股份有限公司 | A kind of preparation method of vistanex rosin molecule common build transparent nucleater |
| CN109164058A (en) * | 2018-08-31 | 2019-01-08 | 北方华锦化学工业股份有限公司 | A kind of method of infrared spectroscopy FTIR detection clarifier NX8000 content |
| CN111300936A (en) * | 2020-02-26 | 2020-06-19 | 江苏斯迪克新材料科技股份有限公司 | High-transmittance protective film for camera |
| CN114854134B (en) * | 2022-05-30 | 2023-08-04 | 会通新材料股份有限公司 | Isotropic low-linearity polypropylene composition, and preparation method and application thereof |
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