CN114561043B - Polypropylene nucleating agent composition, and preparation method and application thereof - Google Patents
Polypropylene nucleating agent composition, and preparation method and application thereof Download PDFInfo
- Publication number
- CN114561043B CN114561043B CN202210361739.XA CN202210361739A CN114561043B CN 114561043 B CN114561043 B CN 114561043B CN 202210361739 A CN202210361739 A CN 202210361739A CN 114561043 B CN114561043 B CN 114561043B
- Authority
- CN
- China
- Prior art keywords
- polypropylene
- nucleating agent
- parts
- agent composition
- bis
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/527—Cyclic esters
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
Abstract
The invention relates to the technical field of polypropylene nucleating agents, and provides a polypropylene nucleating agent composition, a preparation method and an application thereof, wherein the polypropylene nucleating agent composition comprises the following components in parts by weight: 2,2' -methylene-bis (4,6-di-tert-butylbenzoyloxy) sodium phosphate 20-30 parts, calcium stearate 10-15 parts, and bis (dioctyloxypyrophosphate) ethylene titanate 0-1 part. By the technical scheme, the problems that the polypropylene in the prior art is low in transparency and needs to be improved in mechanical property are solved.
Description
Technical Field
The invention relates to the technical field of polypropylene nucleating agents, in particular to a polypropylene nucleating agent composition and a preparation method and application thereof.
Background
Polypropylene (PP) is one of five general-purpose thermoplastic plastics, has low cost and excellent comprehensive performance, is widely applied to various fields of daily life, pipe packaging and the like, and has high growth speed and great development potential in five general-purpose synthetic resins.
However, polypropylene has some disadvantages, such as poor transparency and slow crystallization speed, and the addition of nucleating agent can improve the optical properties, increase the crystallization speed and simultaneously improve the mechanical properties of polypropylene. The nucleating agents commonly used at present are inorganic nucleating agents, metal phosphates, metal carboxylates and sorbitol high-molecular nucleating agents.
The metal phosphate nucleating agent has high melting point, high thermal stability and strong nucleating capability, can improve the mechanical property of polypropylene, but has the problems of poor dispersibility and easy precipitation in the process of modifying polypropylene, and can cause the transparency of polypropylene to be reduced, and the effect of the modified polypropylene is not exerted to the utmost extent due to the poor dispersibility, so that the mechanical property needs to be improved.
Disclosure of Invention
The invention provides a polypropylene nucleating agent composition, and a preparation method and application thereof, and solves the problems that polypropylene in the prior art is low in transparency and needs to be improved in mechanical property.
The technical scheme of the invention is as follows:
a polypropylene nucleating agent composition comprises the following components in parts by weight: 2,2' -methylene-bis (4,6-di-tert-butylbenzoyloxy) sodium phosphate 20-30 parts, calcium stearate 10-15 parts, and bis (dioctyloxypyrophosphate) ethylene titanate 0-1 part.
As a further technical scheme, the polypropylene nucleating agent composition comprises the following components in parts by weight: 2,2' -methylene-bis (4,6-di-tert-butylbenzene oxyl) sodium phosphate 20-30 parts, calcium stearate 10-15 parts, and bis (dioctyloxy pyrophosphate) ethylene titanate 0.2-1 part.
According to the invention, the bis (dioctyloxy pyrophosphate) ethylene titanate and calcium stearate and 2,2' -methylene-bis (4,6-di-tert-butylbenzoyloxy) sodium phosphate are adopted, so that the dispersibility can be improved, the problems of poor dispersibility and easy precipitation of the inorganic nucleating agent are solved, the characteristics of the bis (dioctyloxy pyrophosphate) ethylene titanate and the calcium stearate can be fused together, a synergistic effect is generated, the modification effect of the polypropylene nucleating agent composition on polypropylene is greatly increased, and the transparency and tensile strength of the polypropylene are improved.
As a further technical scheme, the polypropylene nucleating agent composition comprises the following components in parts by weight: 2,2' -methylene-bis (4,6-di-tert-butoxyl) sodium phosphate 25 parts, calcium stearate 12.5 parts, and bis (dioctyloxypyrophosphate) ethylene titanate 0.5 part.
As a further technical scheme, the mass ratio of 2,2' -methylene-bis (4,6-di-tert-butoxyl) sodium phosphate to calcium stearate is 2:1.
The invention also provides a preparation method of the polypropylene nucleating agent composition, which comprises the following steps: adding dimethyl sulfoxide dropwise into 2,2' -methylene-bis (4,6-di-tert-butylbenzene oxyl) sodium phosphate until the dimethyl sulfoxide is dissolved, adding other raw materials, and uniformly mixing.
The invention also provides application of the polypropylene nucleating agent composition in preparation of polypropylene.
As a further technical scheme, the polypropylene nucleating agent composition is added into polypropylene to be mixed and dried, and antioxidant is added to be extruded and injection molded.
As a further technical scheme, the polypropylene nucleating agent composition is 0.1-0.3 part by weight, the polypropylene is 100-120 parts by weight, and the antioxidant is 0.1-0.5 part by weight.
The addition amount of the polypropylene nucleating agent composition needs to be controlled, when the addition amount of the nucleating agent composition is 0.1-0.3 part by weight and exceeds 0.3 part by weight of 100-120 parts by weight of polypropylene, the crystallization rate is too high, the defects caused by incomplete crystallization can be caused, and when the addition amount is less than 0.1 part by weight, the content is too low, the epimorphic crystallization center is incomplete, and the crystal nucleus is incomplete. Preferably, 0.1 part of the polypropylene nucleator composition is added to 100 parts of polypropylene.
As a further technical scheme, the dwell time is 15-18s during the injection molding.
When the polypropylene nucleating agent composition is added to prepare polypropylene, the pressure maintaining time is strictly controlled during injection molding, when the pressure maintaining time is less than 15s, crystallization is incomplete, and when the pressure maintaining time exceeds 18s, more defects appear in the crystallization process, the perfection and regularity of alpha crystal nuclei are influenced, and the transparency is reduced.
The invention has the beneficial effects that:
1. the nucleating agent composition can improve the transparency, tensile strength and dimensional stability of polypropylene, and the prepared polypropylene has the transmittance of 60.8-70.2% and the tensile strength of 22.3-27.1MPa.
2. In the invention, 2,2' -methylene-bis (4,6-di-tert-butylbenzoyloxy) sodium phosphate, calcium stearate and bis (dioctyloxy pyrophosphate) ethylene titanate act synergistically, so that the dispersibility of the metal phosphate is improved, and the prepared polypropylene has high transparency and excellent mechanical properties.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any inventive step, are intended to be within the scope of the present invention.
Example 1
20 parts of 2,2' -methylene-bis (4,6-di-tert-butylphenoxy) sodium phosphate is dissolved in dimethyl sulfoxide till being completely dissolved, 10 parts of calcium stearate is added and uniformly mixed to obtain the polypropylene nucleating agent composition.
Adding 0.1 part of polypropylene nucleating agent composition into 100 parts of polypropylene, mixing and drying, adding 0.1 part of antioxidant 1010, extruding and granulating, and performing injection molding, wherein during injection molding, the melt temperature is controlled at 210 ℃, and the injection rate is 45 m.s -1 And the injection pressure and the pressure maintaining pressure are 50MPa, and the pressure maintaining time is 15s, so that the polypropylene sample is obtained.
Example 2
30 parts of 2,2' -methylene-bis (4,6-di-tert-butylphenoxy) sodium phosphate is dissolved in dimethyl sulfoxide until being completely dissolved, 15 parts of calcium stearate and 1 part of bis (dioctyloxypyrophosphate) ethylene titanate are added and uniformly mixed to obtain the polypropylene nucleating agent composition.
Adding 0.2 part of polypropylene nucleating agent composition into 110 parts of polypropylene, mixing and drying, adding 0.3 part of antioxidant 1010, extruding and granulating, and performing injection molding, wherein during injection molding, the melt temperature is controlled at 215 ℃, and the injection rate is 45 m.s -1 And the injection pressure and the pressure maintaining pressure are 50MPa, and the pressure maintaining time is 16s, so that the polypropylene sample is obtained.
Example 3
25 parts of 2,2' -methylene-bis (4,6-di-tert-butylphenoxy) sodium phosphate is dissolved in dimethyl sulfoxide until being completely dissolved, 12.5 parts of calcium stearate and 0.5 part of bis (dioctyloxypyrophosphate) ethylene titanate are added, and the mixture is uniformly mixed to obtain the polypropylene nucleating agent composition.
Adding 0.2 part of polypropylene nucleating agent composition into 120 parts of polypropylene, mixing and drying, adding 0.3 part of antioxidant 1010, extruding and granulating, and performing injection molding, wherein during injection molding, the melt temperature is controlled at 210 ℃, and the injection rate is 45 m.s -1 And (3) obtaining a polypropylene sample by the injection pressure and the pressure maintaining pressure of 50MPa and the pressure maintaining time of 18s.
Example 4
25 parts of 2,2' -methylene-bis (4,6-di-tert-butylphenoxy) sodium phosphate is dissolved in dimethyl sulfoxide until being completely dissolved, 12.5 parts of calcium stearate and 0.5 part of bis (dioctyloxypyrophosphate) ethylene titanate are added, and the mixture is uniformly mixed to obtain the polypropylene nucleating agent composition.
Adding 0.1 part of polypropylene nucleating agent composition into 100 parts of polypropylene, mixing and drying, adding 0.1 part of antioxidant 1010, extruding and granulating, and performing injection molding to obtain the polypropylene nucleating agent compositionWhen injection molding is carried out, the melt temperature is controlled at 210 ℃, and the injection speed is controlled at 45 m.s -1 And the injection pressure and the pressure maintaining pressure are 50MPa, and the pressure maintaining time is 15s, so that the polypropylene sample is obtained.
Example 5
26 parts of 2,2' -methylene-bis (4,6-di-tert-butylphenoxy) sodium phosphate is dissolved in dimethyl sulfoxide until being completely dissolved, 14 parts of calcium stearate and 0.3 part of bis (dioctyloxypyrophosphate) ethylene titanate are added and uniformly mixed to obtain the polypropylene nucleating agent composition.
Adding 0.1 part of polypropylene nucleating agent composition into 120 parts of polypropylene, mixing and drying, adding 0.4 part of antioxidant 1010, extruding and granulating, and performing injection molding, wherein during injection molding, the melt temperature is controlled at 210 ℃, and the injection rate is 45 m.s -1 And the injection pressure and the pressure maintaining pressure are 50MPa, and the pressure maintaining time is 15s, so that the polypropylene sample is obtained.
Example 6
The pressure holding time was extended to 20s based on example 4, and the rest was the same as example 4.
Comparative example 1
On the basis of example 4, bis (dioctyloxypyrophosphate) ethylene titanate was replaced with an equivalent amount of a silane coupling agent KH560, and the others were the same as in example 4.
Comparative example 2
The polypropylene nucleating agent composition was not added, and the extrusion granulation and injection molding were carried out by the method of example 4 using 100 parts of polypropylene and 0.1 part of antioxidant 1010 as it is.
Examples of the experiments
Tensile strength: carrying out the measurement of the tensile property of the plastic in the GB/T1040.2-2006 standard;
dimensional stability: coupon dimensional stability is expressed by the ratio of the perpendicular melt flow direction (TD) and the parallel melt flow direction (MD) dimensions;
light transmittance: the determination of the light transmittance and haze of the transparent plastic of standard GB/T2410-2008 was carried out.
TABLE 1 comparison of the properties of the examples and comparative examples
The nucleating agent composition provided by the invention not only improves the strength and dimensional stability of polypropylene, but also improves the transparency of polypropylene. Wherein example 4 is the best overall performance example. In example 1, bis (dioctyloxypyrophosphate) ethylene titanate is not added, calcium stearate and 2,2' -methylene-bis (4,6-di-tert-butoxyl) sodium phosphate are compounded to be used as a nucleating agent, and compared with polypropylene without the nucleating agent, the performance of each aspect is improved, but compared with example 4, the improvement degree is lower. In comparative example 1, the use of a silane coupling agent KH560 instead of the bis (dioctyloxypyrophosphate) ethylene titanate of example 4 can improve the light transmittance of polypropylene, but the dispersion effect on polypropylene is inferior to that of example 4, resulting in a lower degree of improvement in transparency, tensile strength and dimensional stability of polypropylene. The dwell time is prolonged in example 6, the transmittance is not increased any more or is reduced even more than that in example 4, and the nucleating agent of the present invention causes crystal nucleus defects when the dwell time reaches 20 s.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (4)
1. The application of the polypropylene nucleating agent composition in preparing polypropylene is characterized in that the polypropylene nucleating agent composition accounts for 0.1 to 0.3 part by weight, the polypropylene accounts for 100 to 120 parts by weight, and the antioxidant accounts for 0.1 to 0.5 part by weight;
the polypropylene nucleating agent composition comprises the following components in parts by weight: 2,2' -methylene-bis (4,6-di-tert-butylbenzene oxyl) sodium phosphate 20-30 parts, calcium stearate 10-15 parts, and bis (dioctyloxy pyrophosphate) ethylene titanate 0.2-1 part;
adding the polypropylene nucleating agent composition into polypropylene, mixing and drying, adding an antioxidant, and performing extrusion injection molding;
and during injection molding, the pressure maintaining time is 15 to 18s.
2. The use of a polypropylene nucleator composition according to claim 1 for preparing polypropylene, wherein the polypropylene nucleator composition comprises the following components in parts by weight: 2,2' -methylene-bis (4,6-di-tert-butoxyl) sodium phosphate 25 parts, calcium stearate 12.5 parts, and bis (dioctyloxypyrophosphate) ethylene titanate 0.5 part.
3. The use of a polypropylene nucleator composition according to claim 1, wherein the mass ratio of 2,2' -methylene-bis (4,6-di-tert-butoxyl) sodium phosphate to calcium stearate is 2:1.
4. The use of the polypropylene nucleating agent composition according to claim 1 for preparing polypropylene, wherein the preparation method of the polypropylene nucleating agent composition comprises the following steps: adding dimethyl sulfoxide dropwise into 2,2' -methylene-bis (4,6-di-tert-butylphenoxy) sodium phosphate until the dimethyl sulfoxide is dissolved, adding other raw materials, and uniformly mixing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210361739.XA CN114561043B (en) | 2022-04-07 | 2022-04-07 | Polypropylene nucleating agent composition, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210361739.XA CN114561043B (en) | 2022-04-07 | 2022-04-07 | Polypropylene nucleating agent composition, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114561043A CN114561043A (en) | 2022-05-31 |
| CN114561043B true CN114561043B (en) | 2023-01-31 |
Family
ID=81721209
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210361739.XA Active CN114561043B (en) | 2022-04-07 | 2022-04-07 | Polypropylene nucleating agent composition, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114561043B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0881592A (en) * | 1994-09-14 | 1996-03-26 | Dainippon Ink & Chem Inc | Colored polypropylene composition |
| JP2010037378A (en) * | 2008-08-01 | 2010-02-18 | Teijin Ltd | Polylactic acid-containing composition and method for producing the same |
| CN103265756A (en) * | 2013-05-07 | 2013-08-28 | 江西吉祥新材料有限公司 | Polypropylene additive composition, and application and polypropylene composition thereof |
| CN106025156A (en) * | 2016-05-19 | 2016-10-12 | 河南师范大学 | Nano plasticized porous polyethylene dry-stretched film for lithium ion batteries and preparation method thereof |
| CN106279966A (en) * | 2015-06-11 | 2017-01-04 | 合肥杰事杰新材料股份有限公司 | A kind of composite polyolefine material being prone to mold pressing dermatoglyph and preparation method thereof |
| CN107614618A (en) * | 2015-08-20 | 2018-01-19 | 株式会社Adeka | Resin additive composition and use its compound resin composition |
| JP2018048264A (en) * | 2016-09-21 | 2018-03-29 | 株式会社Adeka | Method for producing olefinic resin composition, olefinic resin composition and molded product of the same |
| WO2021177386A1 (en) * | 2020-03-06 | 2021-09-10 | 新日本理化株式会社 | Crystal nucleating agent composition for polyolefin resin, and polyolefin resin composition including said crystal nucleating agent composition |
-
2022
- 2022-04-07 CN CN202210361739.XA patent/CN114561043B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0881592A (en) * | 1994-09-14 | 1996-03-26 | Dainippon Ink & Chem Inc | Colored polypropylene composition |
| JP2010037378A (en) * | 2008-08-01 | 2010-02-18 | Teijin Ltd | Polylactic acid-containing composition and method for producing the same |
| CN103265756A (en) * | 2013-05-07 | 2013-08-28 | 江西吉祥新材料有限公司 | Polypropylene additive composition, and application and polypropylene composition thereof |
| CN106279966A (en) * | 2015-06-11 | 2017-01-04 | 合肥杰事杰新材料股份有限公司 | A kind of composite polyolefine material being prone to mold pressing dermatoglyph and preparation method thereof |
| CN107614618A (en) * | 2015-08-20 | 2018-01-19 | 株式会社Adeka | Resin additive composition and use its compound resin composition |
| CN106025156A (en) * | 2016-05-19 | 2016-10-12 | 河南师范大学 | Nano plasticized porous polyethylene dry-stretched film for lithium ion batteries and preparation method thereof |
| JP2018048264A (en) * | 2016-09-21 | 2018-03-29 | 株式会社Adeka | Method for producing olefinic resin composition, olefinic resin composition and molded product of the same |
| WO2021177386A1 (en) * | 2020-03-06 | 2021-09-10 | 新日本理化株式会社 | Crystal nucleating agent composition for polyolefin resin, and polyolefin resin composition including said crystal nucleating agent composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114561043A (en) | 2022-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102952336B (en) | Active basic magnesium sulfate whisker modified polypropylene composite material and preparation method thereof | |
| WO2012061041A1 (en) | Nucleating agent for polyethylenes | |
| CN113088006B (en) | Polypropylene composite master batch and preparation method thereof | |
| CN111454517B (en) | Polypropylene resin special for high-speed biaxially oriented film and preparation method and application thereof | |
| CN113321873B (en) | Low-shrinkage high-toughness modified polypropylene material and preparation method thereof | |
| CN112029256A (en) | Color master batch and preparation method thereof | |
| CN114561043B (en) | Polypropylene nucleating agent composition, and preparation method and application thereof | |
| CN105061902A (en) | Activated carbon fiber modified polypropylene composite material and preparation method thereof | |
| CN109503944B (en) | High-strength acid-alkali-resistant polypropylene composite material and preparation method thereof | |
| CN102850734A (en) | High-transmittance high-shading PET composition and preparation method thereof | |
| CN113278220B (en) | Anti-aging toughening master batch for PP non-woven fabrics and preparation method thereof | |
| CN111378207B (en) | Nucleating agent for polyolefin | |
| CN103804859A (en) | Highlight low-volatile polybutylene terephthalate (PBT) composition as well as preparation method and application of composition | |
| CN112679956A (en) | High-precision low-overflow low-warpage low-dielectric PPS modified material and preparation method thereof | |
| CN108864676B (en) | Weather-resistant matte polycarbonate reclaimed material and preparation method thereof | |
| CN112521741A (en) | Modified polycarbonate with spraying-free effect, ultrahigh weather resistance and high blackness for outdoor use and preparation method thereof | |
| CN107540938B (en) | Modified polypropylene reclaimed material and preparation method thereof | |
| CN114381118B (en) | Thermoplastic polyimide material with high fluidity and low thermal expansion coefficient, preparation method and application thereof | |
| CN112322018B (en) | Transparent antifogging PC resin and preparation method thereof | |
| CN113681755A (en) | Antifogging PET master batch and preparation method thereof | |
| CN114524974B (en) | Nucleating agent composition for transparent polypropylene, application of nucleating agent composition and polypropylene composition | |
| CN102888111B (en) | Manufacturing method of polyphenylene sulfide ceramic alloy | |
| CN110819083B (en) | High-mechanical-property flame-retardant reinforced PET and preparation method thereof | |
| CN109320839B (en) | Photodiffusion polypropylene composite material for LED | |
| CN112812548B (en) | High-temperature-resistant and low-temperature-impact-resistant nylon material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |