CN102226026B - Compound beta-crystal nucleating agent used for polypropylene - Google Patents
Compound beta-crystal nucleating agent used for polypropylene Download PDFInfo
- Publication number
- CN102226026B CN102226026B CN 201110119622 CN201110119622A CN102226026B CN 102226026 B CN102226026 B CN 102226026B CN 201110119622 CN201110119622 CN 201110119622 CN 201110119622 A CN201110119622 A CN 201110119622A CN 102226026 B CN102226026 B CN 102226026B
- Authority
- CN
- China
- Prior art keywords
- beta crystal
- type nucleater
- beta
- crystal
- nucleater
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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 that the application number submitted on March 12nd, 2007 is dividing an application of 200710027115.X, the denomination of invention Chinese patent application that is " a kind of polyacrylic composite beta crystal-type nucleater ".
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 that determines the performances such as its mechanics, 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 states etc.Monoclinic alpha-crystal form is the most stable, and current commercial polypropylene is mainly this type of crystal formation in (being called for short PP), but its toughness is poor, and this is also the poor reason of common PP shock resistance.Beta crystal belongs to hexagonal system, and the PP of this crystal formation has good impelling strength, because of it, aspect toughness reinforcing and manufacture electrical condenser alligatoring film, is having special performance to come into one's own in recent years.Improve the content of beta crystal in PP, the performance of improving PP is of great importance.
Due to the beta crystal of PP, on thermodynamics, be on quasi-steady, kinetics, to be to be unfavorable for a kind of crystal formation generated, under common processing or crystallization condition, be difficult to obtain, only under special conditions, (as the thermograde certain, or shearing action) could form a small amount of beta crystal.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.
With the α nucleator of usually inducing alpha-crystal form, compare, beta crystal-type nucleater has obvious specificity, and the material that only has minority to have special construction just has the brilliant nucleogenesis of β.Mainly contain following four classes for the beta nucleater to really having obvious β crystallization effect or producing considerable influence in this field up till now: 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.; Equations of The Second Kind be history see first-class in the patents such as DE-A-3610644, EP0682066, CN 1004076B 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 calcium pimelate.With the salt that in imido acid and periodictable, II A family metallic element forms, also belong to this type of in EP 0887475, CN 1210103; The 3rd class is a class aryl amide material of Japan new physics and chemistry company report in 1994, mainly comprises phthalic acid Cyclohexamide and naphthalic acid Cyclohexamide; The 4th class is the 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 efficiency and has realized suitability for industrialized production, but compare with α nucleator commonly used, the beta nucleater kind is few and expensive, finds efficiently, beta nucleater cheaply, remains the very important research topic in this field.
For this reason, be necessary to provide a kind of compound beta crystal-type nucleater cheaply, 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 that one or more beta crystal-type nucleater and one or more synergist form, 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 is to be selected from one or more in material as next group: containing material, heterocyclic material and the inorganic powder of 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 material and/or the heterocyclic material containing aromatic nucleus, and 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 compound A, and this compound has following structural formula:
In formula, n=1-4, preferably 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 compound beta crystal-type nucleater of the present invention, beta crystal-type nucleater can refer to 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; Mixture or compound (as calcium stearate/pimelic acid mixture, the calcium pimelate 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., can be also the mixture that several beta crystal-type nucleaters form with any ratio.
The brilliant nucleator of compound β of the present invention, when former beta crystal-type nucleater effective content reduces, still has the brilliant nucleogenesis of β preferably.
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 together with catalyzer before adding matrix, polymerization, or add before extruder grain after polymerization etc.Composite beta crystal-type nucleater no matter with direct method, adds or the master batch method adds, 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 polyacrylic modification or processing, as improved the 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 compound A 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, adding 0.5 part of above-mentioned composite beta crystal-type nucleater REFOX after plasticizing, after mixing 3min, lower sheet, then be molded in 190C the sheet material that 1mm is thick with vulcanizing press, is designated as formula PP0.5REFOX.
Fluorenes-oxadiazole compound A (n=2)
Utilize Perkin-Elmer DSC-7 thermal analyzer (DSC), N
2protection, be 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, records sample melting process for the second time.Near T 154C
1the melting peak that place occurs is the brilliant melting peak of β, and heat content is Δ H
β, near T 167C
2the melting peak that 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 3the height at the peak of three strong diffraction peaks (110) relevant to alpha-crystal form on the wide-angle x-ray diffractogram, (040) and (130), H
β 1it is the height of beta crystal (300) diffraction peak.
Pure PP F401 also makes batten with same process, is denoted as formula PP0, carries out above-mentioned detection.Correlated results is in 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 in 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 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 in 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 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 in 100 parts of PP, and the wide-angle x-ray diffraction experiment shows the relative content k of beta crystal in 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 in 100 parts of PP, and the wide-angle x-ray diffraction experiment shows the relative content k of beta crystal in 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 in 100 parts of PP, and the wide-angle x-ray diffraction experiment shows the relative content k of beta crystal in system
xbe 92%.
Embodiment 7
Other condition is with embodiment 2, but the rare-earth beta crystal-type nucleater is alternative with equivalent phthalic acid Cyclohexamide, the relative content k of beta crystal in final sample
xbe 93%
Embodiment 8
Other condition is with embodiment 2, but the rare-earth beta crystal-type nucleater is alternative with equivalent naphthalic acid Cyclohexamide, the relative content k of beta crystal in final sample
xbe 93%
Embodiment 9
Other condition is with embodiment 2, but the rare-earth beta crystal-type nucleater is alternative with equivalent γ quinacridone dyestuff E3B, the relative content k of beta crystal in final sample
xbe 53%.
Embodiment 10
Other condition is with embodiment 2, but for the rare-earth beta crystal-type nucleater, equivalent calcium stearate/pimelic acid mixture (the two ratio is 1: 1) substitutes, the relative content k of beta crystal in final sample
xbe 93%.
Embodiment 11
Other condition is with embodiment 2, but the rare-earth beta crystal-type nucleater is alternative with the equivalent calcium pimelate, the relative content k of beta crystal in final sample
xbe 94%.
Embodiment 12
Other condition is with embodiment 2, but zeolite substituted to the relative content k of beta crystal in final sample with the equivalent porous silica
xbe 87%.
Embodiment 13
Other condition is with embodiment 2, but zeolite substituted to the relative content k of beta crystal in final sample with equivalent nano rare earth lanthanum trioxide micro mist
xbe 88%.
Embodiment 14
Other condition is with embodiment 2, but zeolite substituted to the relative content k of beta crystal in final sample with the equivalent porous alumina
xbe 87%.
Embodiment 15
Other condition is with embodiment 2, but zeolite is substituted to (particle diameter is in the 5-20nm scope), the relative content k of beta crystal in final sample with the equivalent nano-calcium carbonate
xbe 91%.
Embodiment 16
Other condition is with embodiment 2, but zeolite substituted to the relative content k of beta crystal in final sample with equivalent terephthalic acid calcium
xbe 92%.
Embodiment 17
Other condition is with embodiment 2, but zeolite substituted to the relative content k of beta crystal in 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 large particle diameter (100-500 μ m).
Claims (5)
1. a polyacrylic composite beta crystal-type nucleater, it is characterized in that, described composite beta crystal-type nucleater comprises that one or more beta crystal-type nucleater and one or more synergist form, 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: calcium stearate/pimelic acid mixture, calcium pimelate and rare-earth beta nucleator;
Wherein, described synergist is selected from salt and the inorganic powder of benzene, fluorenes, thiophene, or derivatives thereof or derivatives thereof; Wherein, described inorganic powder is fine, the ultra-fine or nano-powder of 5nm-500 μ m, and is selected from as next group material: rare earth compound powder, calcium carbonate powder, zeolite powder, porous silica and porous alumina.
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, fine, the ultra-fine or nano-powder that described inorganic powder is 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110119622 CN102226026B (en) | 2007-03-12 | 2007-03-12 | Compound beta-crystal nucleating agent used for polypropylene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110119622 CN102226026B (en) | 2007-03-12 | 2007-03-12 | Compound beta-crystal nucleating agent used for polypropylene |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710027115.XA Division CN101265342B (en) | 2007-03-12 | 2007-03-12 | Composite beta crystal-type nucleater of polypropylene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102226026A CN102226026A (en) | 2011-10-26 |
| CN102226026B true CN102226026B (en) | 2013-12-18 |
Family
ID=44807027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110119622 Active CN102226026B (en) | 2007-03-12 | 2007-03-12 | Compound beta-crystal nucleating agent used for polypropylene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102226026B (en) |
Families Citing this family (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 |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1285750A (en) * | 1997-11-14 | 2001-02-28 | 阿斯特拉曾尼卡有限公司 | New composition of matter |
-
2007
- 2007-03-12 CN CN 201110119622 patent/CN102226026B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1285750A (en) * | 1997-11-14 | 2001-02-28 | 阿斯特拉曾尼卡有限公司 | New composition of matter |
Non-Patent Citations (1)
| Title |
|---|
| 张文俊 等.无机粒子对聚丙烯β晶型成核剂体系的晶型影响.《太原理工大学学报》.2006,第37卷(第2期), * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102226026A (en) | 2011-10-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101265342B (en) | Composite beta crystal-type nucleater of polypropylene | |
| CN102086280B (en) | Preparation method of polypropylene nano composite material | |
| CN1061060C (en) | Porous stretched article of polypropylene-based resin and process for its preparation | |
| CN102226026B (en) | Compound beta-crystal nucleating agent used for polypropylene | |
| CN104558821A (en) | Polypropylene composition and polypropylene material as well as application thereof | |
| CN104559149A (en) | Carbon composite high-thermal-conductivity plastic material and preparation method thereof | |
| CN102181092B (en) | Application of carboxylic acid metal salt of tetrahydrophthalic anhydride as nucleating agent for polypropylene beta crystal form | |
| CN100482733C (en) | Beta-crystal polypropylene composition and its preparing method | |
| CN105102523A (en) | Stabilization of polyamide with copper-based metal organic frameworks | |
| CN104098846A (en) | Special high impact resistant polypropylene pipe material | |
| CN1966563B (en) | Beta crystal form polypropylene nucleating agent and polypropylene resin composition containing same | |
| CN103509357A (en) | Environment-friendly asphalt mixture modifier and preparation method thereof | |
| CN101921462A (en) | Polyester/phyllosilicate nano composite material | |
| CN101671460A (en) | High-flexibility high-strength polypropylene composition, preparation method and use thereof | |
| CN105566746A (en) | Polypropylene composition and polypropylene material, as well as application thereof | |
| CN106866636B (en) | Imide β crystal form nucleating agent, and preparation method and application thereof | |
| CN109942953B (en) | Thermal degradation polypropylene gradient phase change heat storage material and preparation method thereof | |
| CN104558847A (en) | Homo-polypropylene beta nucleating agent and preparation method thereof | |
| CN102268197B (en) | Preparation method of modified filling material with high beta-nucleation effect on polypropylene and preparation method of beta-crystal polypropylene or copolymer of beta-crystal polypropylene | |
| CN1304469C (en) | Polypropylene beta crystalline form nucleator and products produced thereof | |
| CN1114651C (en) | Polypropylene beta crystal nucleator and its application | |
| Ma et al. | Novel intercalated nanocomposites of polypropylene/organic‐rectorite/polyethylene‐octene elastomer: Rheology, crystallization kinetics, and thermal properties | |
| CN103665587B (en) | A kind of polypropene composition and polypropylene granules and preparation method thereof and polypropylene pressure pipeline | |
| CN101759967A (en) | Halogen-free warp-resistant PBT of excellent electrical properties and preparing technique thereof | |
| CN109467806A (en) | A kind of preparation method of compound micro-foaming material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee |
Owner name: GUANGDONG WINNER NEW MATERIALS CO., LTD. Free format text: FORMER NAME: WEILINNA FUNCTIONAL MATERIAL CO., LTD., GUANGDONG |
|
| CP01 | Change in the name or title of a patent holder |
Address after: 528521 Guangdong province Foshan city Gaoming Cangjiang Industrial Park West Park District Patentee after: Guangdong Winner New Materials Technology Co., Ltd. Address before: 528521 Guangdong province Foshan city Gaoming Cangjiang Industrial Park West Park District Patentee before: Weilinna Functional Material Co., Ltd., Guangdong |