CN115873402A - Heat-resistant master batch and heat-stable polyamide composition thereof - Google Patents
Heat-resistant master batch and heat-stable polyamide composition thereof Download PDFInfo
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- CN115873402A CN115873402A CN202111159122.1A CN202111159122A CN115873402A CN 115873402 A CN115873402 A CN 115873402A CN 202111159122 A CN202111159122 A CN 202111159122A CN 115873402 A CN115873402 A CN 115873402A
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- heat
- master batch
- resistant master
- resistant
- polyamide composition
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- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 60
- 239000004952 Polyamide Substances 0.000 title claims abstract description 37
- 229920002647 polyamide Polymers 0.000 title claims abstract description 37
- 239000000203 mixture Substances 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 24
- 229920002302 Nylon 6,6 Polymers 0.000 claims abstract description 23
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 22
- 239000005749 Copper compound Substances 0.000 claims abstract description 20
- 150000002366 halogen compounds Chemical class 0.000 claims abstract description 18
- 125000003277 amino group Chemical group 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- -1 phosphine compound Chemical class 0.000 claims description 8
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 6
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 4
- 239000000654 additive Substances 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 4
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 claims description 4
- 150000004699 copper complex Chemical class 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 2
- ICVUZKQDJNUMKC-UHFFFAOYSA-N [cyclohexyl(phenyl)phosphoryl]benzene Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1CCCCC1 ICVUZKQDJNUMKC-UHFFFAOYSA-N 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 239000003446 ligand Substances 0.000 claims description 2
- IIOSDXGZLBPOHD-UHFFFAOYSA-N tris(2-methoxyphenyl)phosphane Chemical compound COC1=CC=CC=C1P(C=1C(=CC=CC=1)OC)C1=CC=CC=C1OC IIOSDXGZLBPOHD-UHFFFAOYSA-N 0.000 claims description 2
- OUMZKMRZMVDEOF-UHFFFAOYSA-N tris(trimethylsilyl)phosphane Chemical compound C[Si](C)(C)P([Si](C)(C)C)[Si](C)(C)C OUMZKMRZMVDEOF-UHFFFAOYSA-N 0.000 claims description 2
- 229940076286 cupric acetate Drugs 0.000 claims 1
- 230000000704 physical effect Effects 0.000 abstract description 5
- 230000006866 deterioration Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 239000003381 stabilizer Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 239000012760 heat stabilizer Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 2
- 150000002896 organic halogen compounds Chemical class 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000007539 photo-oxidation reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920006039 crystalline polyamide Polymers 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000008642 heat stress Effects 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920006122 polyamide resin Polymers 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Abstract
The invention relates to a heat-resistant master batch and a heat-stable polyamide composition thereof, wherein the heat-resistant master batch contains at least one copper compound, at least one halogen compound and a base material, and the molar ratio of the copper compound to the halogen compound is 1: 10-1: 15, the base material accounts for 55-85% of the total mass of the heat-resistant master batch. The heat-stable polyamide composition comprises 1-1.5% by mass of the heat-resistant master batch and the balance of polyamide 66. The heat-resistant master batch can effectively improve the heat resistance of the polyhexamethylene adipamide without causing the deterioration of the physical properties of the material, and the heat-stable polyamide composition containing the master batch can still keep excellent physical properties after being used in a high-temperature environment for a long time so as to overcome the technical defect of poor stability of the existing polyamide in the high-temperature environment.
Description
Technical Field
The invention relates to a heat-resistant master batch and a heat-stable polyamide composition thereof, in particular to a heat-resistant master batch capable of improving the heat stability of polyamide, a heat-stable polyamide composition containing the master batch, and preparation and application thereof.
Background
Polyhexamethylene adipamide is taken as a high-crystalline polyamide, the material has certain heat resistance, and the material can be used in the fields with requirements on thermal oxidation and photooxidation of the material, such as the production of tire cords, membrane removing cloth, airbag yarns and injection molding parts around engines, wherein the usage amount is the largest in the fields of automobiles and electronics. However, the material is still easy to be oxidized and decomposed when being used in a high-temperature environment for a long time, so that the material loses elasticity, becomes hard and brittle, and further the strength of the product is sharply reduced, and the product cannot be used continuously. At present, the copper-based heat stabilizer is a stabilizer commonly used for high-temperature resistant polyamide, and the copper-based heat stabilizer generally comprises two parts: copper compounds as primary stabilizers and halogen compounds as synergists. The heat stress of the product in a high-temperature environment can be improved by adding the copper heat stabilizer into the conventional polyhexamethylene adipamide, so that the degradation of the material under the thermal and photo-oxidation is slowed down, and the service life of the material is prolonged.
However, copper based stabilizers also present some serious disadvantages: (1) The commonly used copper compounds include cuprous halide, inorganic or organic copper salt, copper complex and the like, the halogen compound includes inorganic halogen compound or organic halogen compound, and the combination of different kinds of copper compound and halogen compound has obvious difference on the stabilizing effect of polyamide, for example: the inorganic halogen compound is matched with the copper compound, so that the dispersion effect of the copper compound in polyamide is poor; the organic halogen compound and the copper compound are adopted to be matched, although the dispersibility of the copper compound can be improved, the heat stability effect is not as good as the compounding effect of the inorganic halogen compound and the copper compound. (2) Because the conventional copper stabilizer is powdery and has a generally small addition amount, the stabilizer is easy to agglomerate in polyamide in the addition process and the addition amount of the stabilizer is difficult to accurately control, the distribution of the stabilizer is easy to be uneven, and the heat-resistant effect of the product cannot reach the expected value. In addition, even if the stabilizer can be uniformly dispersed in the polyamide, since the grain size of the stabilizer is different from that of the polyamide, the crystallization effect affecting the polyamide itself has some negative effects on the physical properties of the product, resulting in deterioration of mechanical properties such as impact strength, tensile strength, etc. of the polyamide resin.
Disclosure of Invention
The technical problem is as follows: the invention aims to provide a heat-resistant master batch and a heat-stable polyamide composition thereof, wherein the heat-resistant master batch can effectively improve the heat resistance of polyhexamethylene adipamide without causing the deterioration of the physical properties of materials, and the heat-stable polyamide composition containing the master batch can still maintain excellent physical properties after being used in a high-temperature environment for a long time so as to overcome the technical defect of poor stability of the conventional polyamide in the high-temperature environment.
The technical scheme is as follows: the heat-resistant master batch contains at least one copper compound, at least one halogen compound and a base material, wherein the molar ratio of the copper compound to the halogen compound is 1: 10-1: 15, the base material accounts for 55-85% of the total mass of the heat-resistant master batch.
Wherein, the first and the second end of the pipe are connected with each other,
the base material is polyhexamethylene adipamide with the relative viscosity of 2.1-2.6 and the content of terminal amino groups of 25-45 mmol/kg.
The relative viscosity of the base stock is 2.2-2.4.
The copper compound is a copper complex, namely a complex formed by copper salt containing cuprous iodide and/or copper acetate and phosphine compound and/or mercaptobenzimidazole compound, wherein the molar ratio of copper to ligand is 1:3 to 1:5.
the phosphine compound is selected from one or more of triphenylphosphine, tri (o-methoxyphenyl) phosphine, cyclohexyl diphenyl phosphine oxide, tri-tert-butylphosphine and tri (trimethylsilyl) phosphine.
The halogen compound is a mixture of potassium iodide and potassium bromide, and the molar ratio of bromine to iodine is 1:3-1:5.
the heat-stable polyamide composition containing the heat-resistant master batch comprises 1-1.5% by mass of the heat-resistant master batch and the balance of polyamide 66.
The relative viscosity of the polyamide 66 is 2.55-2.75, and the content of the terminal amino groups is 35-50 mmol/kg.
The heat stable polyamide composition further comprises conventional additives, UV stability, processing aids, nucleating additives, flow improvers.
The heat-stable polyamide composition containing the heat-resistant master batch is obtained by mixing the heat-resistant master batch and polyamide 66 melt at 255-270 ℃.
Has the advantages that: according to the invention, the copper compound and the specific halogen compound are compounded, and the heat-resistant master batch is obtained from the low-viscosity base material, so that the problem of dispersibility of the inorganic copper salt in the polyamide 66 is effectively solved, and more importantly, the heat resistance of the polyamide 66 composition is obviously improved.
Detailed Description
The principles and features of the present invention are described below in conjunction with the following examples. The examples are given to facilitate a better understanding of the invention by those skilled in the art. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
All of the starting materials referred to in the examples of the present invention are commercially available.
(1) Heat-resistant master batch
The detailed raw materials and the proportion of the heat-resistant master batch of the embodiment and the comparative example are shown in the table 1.
Table 1:
the preparation method of the heat-resistant master batch comprises the following steps:
adding the raw materials into a double-screw extruder, and mixing for 3-5 min at 265-295 ℃ to obtain the heat-resistant master batch.
(2) Heat-stable polyamide composition
The detailed raw materials and the proportions of the heat-stable polyamide compositions of the examples of the present invention are shown in Table 2.
Table 2:
| polyamide composition | Heat-resistant master batch | Mass fraction/% of the heat-resistant master batch in the composition |
| Example 1 | Heat-resistant masterbatch 1 | 1.5 |
| Example 2 | Heat-resistant master batch 2 | 1.5 |
| Example 3 | Heat-resistant masterbatch 3 | 1.2 |
| Example 4 | Heat-resistant masterbatch 4 | 1 |
| Example 5 | Heat-resistant master batch 2 | 1.5 |
| Example 6 | Heat-resistant master batch 2 | 1.5 |
| Example 7 | Heat-resistant master batch 5 | 1.5 |
| Example 8 | Heat-resistant master batch 6 | 1.5 |
| Example 9 | Heat-resistant masterbatch 7 | 1 |
| Example 10 | Heat-resistant master batch 8 | 1 |
| Example 11 | Heat-resistant master batch 9 | 1 |
| Example 12 | Heat-resistant masterbatch 10 | 1 |
Wherein, the polyamides adopted in the heat-stable polyamide composition of the embodiment of the invention are all polyamide 66, the relative viscosity is 2.65, and the content of the terminal amino groups is 45mmol/kg.
In the examples of the present invention, the heat-stable polyamide composition was prepared as follows: the heat-resistant master batch is melted by a double screw and then conveyed into a polyamide 66 melt pipeline to be mixed, and the temperature is 260-270 ℃.
Comparative example 1
The polyamide composition does not contain the heat-resistant master batch, is only pure polyamide 66, and has the relative viscosity of 2.65 and the content of terminal amino groups of 45mmol/kg.
Comparative example 2
The difference from example 1 is that the heat-resistant master batch does not contain a binder, and the copper compound and the halogen compound are directly added to the polyamide 66 in the form of powder.
Comparative example 3
The difference from example 2 is that the base material in the heat-resistant master batch was replaced with polyamide 66 having a relative viscosity of 2.0 and a terminal amino group content of 25.
Comparative example 4
The difference from example 2 is that the base material in the heat-resistant master batch was replaced with polyamide 66 having a relative viscosity of 2.67 and a terminal amino group content of 41.
Comparative example 5
The difference from example 2 is that the base material in the heat-resistant master batch was replaced with polyamide 66 having a relative viscosity of 2.4 and a terminal amino group content of 15.
Comparative example 6
The difference from example 2 is that the base material in the heat-resistant master batch was replaced with polyamide 66 having a relative viscosity of 2.4 and a terminal amino group content of 60.
Comparative example 7
The difference from example 3 is that the molar ratio of the copper compound to the halogen compound in the heat-resistant mother particle is 1:8.
comparative example 8
The difference from example 3 is that the molar ratio of the copper compound to the halogen compound in the heat-resistant mother particle is 1:17.
the data of the performance tests of the examples and comparative examples are shown in Table 3:
table 3:
the performance test method comprises the following steps:
the relative viscosity test method of the polyamide adopts GB/T1632.1-2008 test.
The content of the terminal amino group is tested by adopting a potentiometric titration method.
Thermal aging time: at an initial strain rate of 0.1mm/min, the material reaches its embrittlement end point when 75% of the samples tested have an elongation at break of 20% or less, the time required for the material to reach the embrittlement end point being referred to as the heat ageing time.
Copper content tolerance value: in the experimental process, 6 times of sampling are carried out to test the difference between the maximum value and the minimum value of the copper content, so as to evaluate the distribution uniformity of the auxiliary agent, the smaller the difference value is, the better the uniformity is, and the larger the difference value is, the worse the uniformity is; the method for testing the copper content comprises the following steps: weighing 50mg of sample, digesting the sample by using 6mL of concentrated nitric acid microwave, and determining by using an inductively coupled plasma mass spectrometer.
Notch impact test: adjusting the state in a constant temperature and humidity box, testing the notch impact strength according to GB/T1043.1-2008 after the temperature is 23 +/-1 ℃, the humidity is 50 +/-5 percent and 48 hours.
Claims (10)
1. The heat-resistant master batch is characterized by comprising at least one copper compound, at least one halogen compound and a base material, wherein the molar ratio of the copper compound to the halogen compound is 1: 10-1: 15, the base material accounts for 55-85% of the total mass of the heat-resistant master batch.
2. The heat-resistant master batch according to claim 1, wherein the base material is polyhexamethylene adipamide having a relative viscosity of 2.1-2.6 and a terminal amino group content of 25-45 mmol/kg.
3. The heat-resistant masterbatch according to claim 2, wherein the binder has a relative viscosity of 2.2-2.4.
4. The heat-resistant master batch according to claim 1, wherein the copper compound is a copper complex formed by a copper salt containing cuprous iodide and/or cupric acetate and a phosphine compound and/or a mercaptobenzimidazole compound, wherein the molar ratio of copper to ligand is 1:3 to 1:5.
5. the heat-resistant masterbatch according to claim 4, wherein the phosphine compound is at least one selected from triphenylphosphine, tris (o-methoxyphenyl) phosphine, cyclohexyldiphenylphosphine oxide, tri-t-butylphosphine, and tris (trimethylsilyl) phosphine.
6. The heat-resistant master batch according to claim 1, wherein the halogen compound is a mixture of potassium iodide and potassium bromide, and the molar ratio of bromine to iodine is 1:3-1:5.
7. a heat-stable polyamide composition comprising the heat-resistant master batch according to claim 1, wherein the heat-stable polyamide composition comprises 1 to 1.5% by mass of the heat-resistant master batch and the balance of polyamide 66.
8. The heat-stable polyamide composition containing the heat-resistant master batch according to claim 7, wherein the polyamide 66 has a relative viscosity of 2.55 to 2.75 and a content of terminal amino groups of 35 to 50mmol/kg.
9. The heat-stable polyamide composition containing the heat-resistant masterbatch of claim 7, wherein the heat-stable polyamide composition further comprises conventional additives, UV stability, processing aids, nucleating additives, flow improvers.
10. The heat-stable polyamide composition containing a heat-resistant master batch according to claim 7, wherein the heat-stable polyamide composition containing a heat-resistant master batch is obtained by mixing the heat-resistant master batch and polyamide 66 melt at 255 to 270 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111159122.1A CN115873402A (en) | 2021-09-30 | 2021-09-30 | Heat-resistant master batch and heat-stable polyamide composition thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111159122.1A CN115873402A (en) | 2021-09-30 | 2021-09-30 | Heat-resistant master batch and heat-stable polyamide composition thereof |
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| Publication Number | Publication Date |
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| CN115873402A true CN115873402A (en) | 2023-03-31 |
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| CN202111159122.1A Pending CN115873402A (en) | 2021-09-30 | 2021-09-30 | Heat-resistant master batch and heat-stable polyamide composition thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3491042A (en) * | 1966-03-12 | 1970-01-20 | Bayer Ag | Stabilized polyamide composition containing copper salts and metal cyanides |
| CN1326481A (en) * | 1998-10-15 | 2001-12-12 | L·布鲁克曼两合公司 | Polyamide composition stabilized with copper complexes and organic halogen compounds |
| US20130274399A1 (en) * | 2010-10-18 | 2013-10-17 | Dsm Ip Assets B.V. | Heat stabilized polyamide composition |
-
2021
- 2021-09-30 CN CN202111159122.1A patent/CN115873402A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3491042A (en) * | 1966-03-12 | 1970-01-20 | Bayer Ag | Stabilized polyamide composition containing copper salts and metal cyanides |
| CN1326481A (en) * | 1998-10-15 | 2001-12-12 | L·布鲁克曼两合公司 | Polyamide composition stabilized with copper complexes and organic halogen compounds |
| US20130274399A1 (en) * | 2010-10-18 | 2013-10-17 | Dsm Ip Assets B.V. | Heat stabilized polyamide composition |
Non-Patent Citations (1)
| Title |
|---|
| 曹可生;徐伏;段甲欣;曹倩;任永德;: "PA66抗热氧化技术在聚合工艺中的应用", 广西轻工业, no. 10, pages 31 - 32 * |
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