CN102226026A - Compound beta-crystal nucleating agent used for polypropylene - Google Patents
Compound beta-crystal nucleating agent used for polypropylene Download PDFInfo
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- CN102226026A CN102226026A CN2011101196222A CN201110119622A CN102226026A CN 102226026 A CN102226026 A CN 102226026A CN 2011101196222 A CN2011101196222 A CN 2011101196222A CN 201110119622 A CN201110119622 A CN 201110119622A CN 102226026 A CN102226026 A CN 102226026A
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Abstract
The present invention discloses a compound beta-crystal nucleating agent used for polypropylene processing, which is composed of 100 parts by weight of one or more beta-crystal nucleating agents and 0.0001-1000 parts (preferably 1-200 parts) by weight of one or more synergists. Since the existence of the synergist, a series of high-efficiency low-cost compound beta-crystal nucleating agents are expected to be obtained. The compound beta-crystal nucleating agent is expected to be widely applied in the fields of automobiles, pipelines, films, electrical and electronic appliances, etc.
Description
The division statement
The application is the application number submitted on March 12nd, 2007 the dividing an application for the Chinese patent application of " a kind of polyacrylic composite beta crystal-type nucleater " that be 200710027115.X, denomination of invention.
Technical field
The present invention relates to a kind of compound beta crystal-type nucleater of polypropylene processing.
Background technology
For the crystalline polymer polypropylene, crystallization property is the important factor of performances such as its mechanics of decision, optics.The molecular chain of isotatic polypropylene is 3 helicoidal configurations, and crystalline structure can form five kinds of α, β, γ, δ and plan six side's attitudes etc.Monoclinic alpha-crystal form is the most stable, and present commercial polypropylene is mainly this type of crystal formation in (being called for short PP), but its toughness is relatively poor, and this also is the reason of common PP shock resistance difference.Beta crystal belongs to hexagonal system, and the PP of this crystal formation has good impelling strength, is having special performance to come into one's own because of it aspect toughness reinforcing and the manufacturing electrical condenser alligatoring film in recent years.Improve the content of beta crystal among the PP, the performance of improving PP is of great importance.
Because the beta crystal of PP is being to be to be unfavorable for a kind of crystal formation of generating on quasi-steady, the kinetics on the thermodynamics, under common processing or crystallization condition, be difficult to obtain, only (as in certain thermograde, or shearing action) could form a small amount of beta crystal under special conditions.Add some can induce what is called " beta crystal-type nucleater " of generating beta crystal (or claim " beta nucleater ") but be can obtain the high-content beta crystal, also be the approach of unique industrializing implementation at present.
Compare with the α nucleator of inducing alpha-crystal form usually, beta crystal-type nucleater has tangible specificity, and the material that promptly has only minority to have special construction just has the brilliant nucleogenesis of β.Up till now for mainly containing following four classes to the beta nucleater that really has obvious β crystallization effect or produce considerable influence in this field: the first kind is the fused ring compound that minority has the directrix plane structure, as γ quinacridone γ-Quinacridone dyestuff E3B, triphen dithiazine Triphenodithiazine etc.; Second class be history see first-class in patents such as DE-A-3610644, EP0682066, CN 1004076B the mixture or the compound of the salt of disclosed some IIa family element or itself and specific di-carboxylic acid, typically example is calcium stearate/pimelic acid mixture or pimelic acid calcium.The salt that forms with II A family metallic element in imido acid and the periodictable among EP 0887475, the CN 1210103 also belongs to this type of; The 3rd class is a class aryl amide material of the new physics and chemistry company of Japan report in 1994, mainly comprises phthalic acid Cyclohexamide and naphthalic acid Cyclohexamide; The 4th class is a disclosed rare earth compounding class beta nucleater in Chinese patent ZL00117339.1 such as Feng Jiachun.Although third and fourth class nucleator has very high nucleation efficient and has realized suitability for industrialized production, but compare with α nucleator commonly used, the beta nucleater kind is few and cost an arm and a leg, and seeks efficiently, beta nucleater cheaply, remains the crucial research topic in this field.
For this reason, be necessary to provide a kind of compound cheaply beta crystal-type nucleater, it can reduce effective usage quantity of expensive beta crystal-type nucleater, but still has good nucleogenesis.
Summary of the invention
The purpose of this invention is to provide a kind of compound beta crystal-type nucleater, this compound beta crystal-type nucleater can reduce effective usage quantity of beta crystal-type nucleater.
In order to realize above-mentioned goal of the invention, the invention provides a kind of polyacrylic composite beta crystal-type nucleater, this composite beta crystal-type nucleater comprises one or more beta crystal-type nucleater and one or more synergist composition, wherein, by weight, the ratio of beta crystal-type nucleater and synergist is 99.50: 0.50～1.00: 99.00, is preferably 95.00: 5.00～5.00: 95.00; Synergist then is to be selected from as next group one or more in material: the material, heterocyclic material and the inorganic powder that contain aromatic nucleus; Wherein, inorganic powder can be fine, the ultra-fine or nano-powder of 5nm-500 μ m, is preferably fine, the ultra-fine or nano-powder of 10nm-100 μ m.
Preferably, in above-mentioned composite beta crystal-type nucleater, the ratio of beta crystal-type nucleater and synergist is 90.00: 10.00～10.00: 90.00; More preferably, the ratio of beta crystal-type nucleater and synergist is 90.00: 10.00～30.00: 70.00.
In composite beta crystal-type nucleater of the present invention, synergist can be organic material, as contains the material and/or the heterocyclic material of aromatic nucleus, more specifically can be as the salt of benzene, fluorenes, thiophene, or derivatives thereof or derivatives thereof.A kind of concrete synergist can be fluorenes-oxadiazole compd As, and this compound has following structural formula:
In the formula, n=1-4, preferred n=2.
In composite beta crystal-type nucleater of the present invention, synergist can be fine, ultra-fine or nano level inorganic powder, as rare earth compound powder, some calcium carbonate powder etc.For inorganic powder class synergist, what its size can be at 1nm-500 μ m, be preferably fine, the ultra-fine or nano-powder of 5nm-500 μ m, more preferably fine, the ultra-fine or nano-powder of 10nm-100 μ m.Synergist of the present invention can also be mesoporous material especially, as zeolite powder, porous silica, porous alumina etc.
In the compound beta crystal-type nucleater of the present invention, beta crystal-type nucleater can be meant that all have the material of obvious beta crystal nucleogenesis, include but not limited to: the fused ring compound class beta crystal-type nucleater (as γ quinacridone γ-Quinacridone dyestuff, triphen dithiazine Triphenodithiazine etc.) with directrix plane structure; The mixture or compound (as calcium stearate/pimelic acid mixture, the pimelic acid calcium etc.) beta crystal-type nucleater of the salt of some IIa family element or itself and specific di-carboxylic acid; Aromatic amides class beta crystal-type nucleater (as phthalic acid Cyclohexamide and naphthalic acid Cyclohexamide etc.); And the rare earth beta crystal-type nucleater etc., also can be the mixture that several beta crystal-type nucleaters form with any ratio.
The brilliant nucleator of compound β of the present invention still has the brilliant nucleogenesis of β preferably when former beta crystal-type nucleater effective content reduces.
Composite nucleating agent of the present invention can with conventional Process Technology of Polymer method disperse with macromolecule matrix in, as make master batch and add matrix, directly add with catalyzer before adding matrix, polymerization, or after polymerization, add before the extruder grain etc.No matter composite beta crystal-type nucleater adds or the adding of master batch method with direct method, and its final consumption in the matrix polypropylene is 0.00001～90% (weight ratio), is preferably in 0.001-50%.
Utilize the present invention to be expected to obtain a series of efficient and low-cost beta crystal-type nucleaters, can be used for MODIFICATION OF POLYPROPYLENE or processing, as improving aspects such as toughness, raising heat-drawn wire, formation micropore.
By the following examples the present invention is further described, wherein form umber, content all by weight.
Embodiment
Embodiment 1
90 parts of rare earth beta crystal-type nucleaters, 10 parts of fluorenes-oxadiazole compd As that structure is illustrated in fig. 1 shown below form composite beta crystal-type nucleater REFOX;
(trade mark F401 melts body flow rate 2.5g/10min, density 0.91g/cm to 100 parts of polypropylene
3) mixing in 170C with two roller mills, the plasticizing back adds 0.5 part of above-mentioned composite beta crystal-type nucleater REFOX, mixes behind the 3min sheet down, is molded into the thick sheet material of 1mm with vulcanizing press in 190C then, is designated as the PP0.5REFOX that fills a prescription.
Fluorenes-oxadiazole compd As (n=2)
Utilize Perkin-Elmer DSC-7 thermal analyzer (DSC), N
2Protection is heated to 200C with the scanning speed of 10C/min from room temperature, and constant temperature 5min is cooled to 30C with 10C/min speed after eliminating thermal history, and the scanning speed with 10C/min is heated to 200C again, and the record sample is melting process for the second time.Near the T 154C
1The melting peak that the place occurs is the brilliant melting peak of β, and heat content is Δ H
β, near the T 167C
2The melting peak that the place occurs is the brilliant melting peak of α, and heat content is Δ H
α, the relative content of beta crystal is calculated by following formula (1),
k
DSC＝ΔH
β/(ΔH
α+ΔH
β) (1)
The relative content of beta crystal often also by wide-angle x-ray diffraction (WAXD), utilizes following Turner-Jones formula (2) to try to achieve simultaneously:
k
x＝H
β1/(H
β1+H
α1+H
α2+H
α3) (1)
H
α 1, H
α 2, H
α 3Be the height at the peak of three strong diffraction peaks (110) relevant on the wide-angle x-ray diffractogram, (040) and (130) with alpha-crystal form, H
β 1It is the height of beta crystal (300) diffraction peak.
Pure PP F401 also makes batten with same process, and note is made prescription PP0, carries out above-mentioned detection.Correlated results sees Table 1.
Table 1 different ingredients each crystal formation content and crystallization rate
Embodiment 2
90 parts of rare earth beta crystal-type nucleaters, 1 part of zeolite molecular sieve (particle size distribution range is mainly at 4-10 μ m) form composite beta crystal-type nucleater REF90/10; 0.01 part of this composite beta crystal-type nucleater REF90/10 is added among 100 parts of PP, and other condition is all same with embodiment 1.The wide-angle x-ray diffraction experiment shows the relative content k of beta crystal in the system
xBe 92%.
Embodiment 3
99.5 part rare earth beta crystal-type nucleater, 0.5 part of zeolite molecular sieve (particle size distribution range is mainly at 3-4 μ m) form composite beta crystal-type nucleater; 0.001 part of this composite beta crystal-type nucleater REF90/10 is added among 100 parts of PP, and other condition is all same with embodiment 1.The wide-angle x-ray diffraction experiment shows the relative content k of beta crystal in the system
xBe 90%.
Embodiment 4
Other condition is with embodiment 2, and the proportioning of rare earth beta crystal-type nucleater and zeolite molecular sieve is 70/30; 0.05 part of this composite beta crystal-type nucleater is added among 100 parts of PP, and the wide-angle x-ray diffraction experiment shows the relative content k of beta crystal in the system
xBe 90%.
Embodiment 5
Other condition is with embodiment 2, and the proportioning of rare earth beta crystal-type nucleater and zeolite molecular sieve is 30/70; 0.5 part of this composite beta crystal-type nucleater is added among 100 parts of PP, and the wide-angle x-ray diffraction experiment shows the relative content k of beta crystal in the system
xBe 88%.
Embodiment 6
Other condition is with embodiment 2, and the proportioning of rare earth beta crystal-type nucleater and zeolite molecular sieve is 5/95; 15 parts of these composite beta crystal-type nucleaters are added among 100 parts of PP, and the wide-angle x-ray diffraction experiment shows the relative content k of beta crystal in the system
xBe 92%.
Embodiment 7
Other condition is with embodiment 2, but the rare earth beta crystal-type nucleater substitutes the relative content k of beta crystal in the final sample with equivalent phthalic acid Cyclohexamide
xBe 93%
Embodiment 8
Other condition is with embodiment 2, but the rare earth beta crystal-type nucleater substitutes the relative content k of beta crystal in the final sample with equivalent naphthalic acid Cyclohexamide
xBe 93%
Embodiment 9
Other condition is with embodiment 2, but the rare earth beta crystal-type nucleater substitutes the relative content k of beta crystal in the final sample with equivalent γ quinacridone dyestuff E3B
xBe 53%.
Embodiment 10
Other condition is with embodiment 2, but the rare earth beta crystal-type nucleater substitutes the relative content k of beta crystal in the final sample with equivalent calcium stearate/pimelic acid mixture (the two ratio is 1: 1)
xBe 93%.
Embodiment 11
Other condition is with embodiment 2, but the rare earth beta crystal-type nucleater substitutes the relative content k of beta crystal in the final sample with equivalent pimelic acid calcium
xBe 94%.
Embodiment 12
Other condition is with embodiment 2, but zeolite substituted the relative content k of beta crystal in the final sample with the equivalent porous silica
xBe 87%.
Embodiment 13
Other condition is with embodiment 2, but zeolite is substituted the relative content k of beta crystal in the final sample with equivalent nano rare earth lanthanum trioxide micro mist
xBe 88%.
Embodiment 14
Other condition is with embodiment 2, but zeolite substituted the relative content k of beta crystal in the final sample with the equivalent porous alumina
xBe 87%.
Embodiment 15
Other condition is with embodiment 2, but zeolite is substituted (particle diameter is in the 5-20nm scope), the relative content k of beta crystal in the final sample with the equivalent nano-calcium carbonate
xBe 91%.
Embodiment 16
Other condition is with embodiment 2, but zeolite is substituted the relative content k of beta crystal in the final sample with equivalent terephthalic acid calcium
xBe 92%.
Embodiment 17
Other condition is with embodiment 2, but zeolite is substituted the relative content k of beta crystal in the final sample with equivalent terephthalic acid Cyclohexamide
xBe 96%.
Embodiment 18
Other condition is with embodiment 2, and the proportioning of rare earth beta crystal-type nucleater and zeolite molecular sieve is 70/30, and selects the zeolite of big particle diameter (100-500 μ m) for use.
Claims (7)
1. polyacrylic composite beta crystal-type nucleater, it is characterized in that, described composite beta crystal-type nucleater comprises one or more beta crystal-type nucleater and one or more synergist composition, wherein, by weight, the ratio of described beta crystal-type nucleater and described synergist is 99.50: 0.50～1.00: 99.00;
Wherein, described beta crystal-type nucleater is selected from as next group material:
Fused ring compound class beta crystal-type nucleater with directrix plane structure;
The IIa family beta crystal-type nucleater that the salt of I Ia family element or itself and di-carboxylic acid form;
Aromatic amides class beta crystal-type nucleater; And
The rare earth beta nucleater;
Wherein, described synergist is selected from inorganic powder, and this inorganic powder is fine, the ultra-fine or nano-powder of 5nm-500 μ m.
2. composite beta crystal-type nucleater as claimed in claim 1 is characterized in that, the ratio of described beta crystal-type nucleater and described synergist is 95.00: 5.00～5.00: 95.00.
3. composite beta crystal-type nucleater as claimed in claim 1 is characterized in that, described inorganic powder is fine, the ultra-fine or nano-powder of 10nm-100 μ m.
4. composite beta crystal-type nucleater as claimed in claim 1 is characterized in that, the ratio of described beta crystal-type nucleater and described synergist is 90.00: 10.00～10.00: 90.00.
5. composite beta crystal-type nucleater as claimed in claim 4 is characterized in that, the ratio of described beta crystal-type nucleater and described synergist is 90.00: 10.00～30.00: 70.00.
6. composite beta crystal-type nucleater as claimed in claim 1 is characterized in that, described synergist is rare earth compound powder, calcium carbonate powder, zeolite powder, porous silica or porous alumina.
7. composite beta crystal-type nucleater as claimed in claim 1 is characterized in that, described fused ring compound class beta crystal-type nucleater is γ quinacridone or triphen dithiazine; Described aromatic amides class beta crystal-type nucleater is phthalic acid Cyclohexamide and/or naphthalic acid Cyclohexamide; Described IIa family beta crystal-type nucleater is pimelic acid calcium or calcium stearate/pimelic acid mixture.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558847A (en) * | 2015-01-07 | 2015-04-29 | 方文川 | Homo-polypropylene beta nucleating agent and preparation method thereof |
| CN106188877A (en) * | 2016-09-05 | 2016-12-07 | 聊城大学 | A kind of β crystalline substance PPR pipe and preparation method |
| CN106380698A (en) * | 2016-09-05 | 2017-02-08 | 聊城大学 | Beta-crystal PPR pipe fitting and production method thereof |
| CN117164932A (en) * | 2023-10-31 | 2023-12-05 | 汕头市虹桥包装实业有限公司 | Injection molding foaming polypropylene material, preparation method thereof and application thereof in lightweight high-performance bottle cap |
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| SE9704186D0 (en) * | 1997-11-14 | 1997-11-14 | Astra Ab | New composition of matter |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558847A (en) * | 2015-01-07 | 2015-04-29 | 方文川 | Homo-polypropylene beta nucleating agent and preparation method thereof |
| CN106188877A (en) * | 2016-09-05 | 2016-12-07 | 聊城大学 | A kind of β crystalline substance PPR pipe and preparation method |
| CN106380698A (en) * | 2016-09-05 | 2017-02-08 | 聊城大学 | Beta-crystal PPR pipe fitting and production method thereof |
| CN117164932A (en) * | 2023-10-31 | 2023-12-05 | 汕头市虹桥包装实业有限公司 | Injection molding foaming polypropylene material, preparation method thereof and application thereof in lightweight high-performance bottle cap |
| CN117164932B (en) * | 2023-10-31 | 2024-01-26 | 汕头市虹桥包装实业有限公司 | Injection molding foaming polypropylene material, preparation method thereof and application thereof in lightweight high-performance bottle cap |
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