CN106479040A - Combined type tranquilizer constituent and modified polymeric material - Google Patents
Combined type tranquilizer constituent and modified polymeric material Download PDFInfo
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- CN106479040A CN106479040A CN201610095322.8A CN201610095322A CN106479040A CN 106479040 A CN106479040 A CN 106479040A CN 201610095322 A CN201610095322 A CN 201610095322A CN 106479040 A CN106479040 A CN 106479040A
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- 239000000463 material Substances 0.000 title claims abstract description 40
- 239000000470 constituent Substances 0.000 title claims abstract description 31
- 229940125725 tranquilizer Drugs 0.000 title claims abstract description 29
- 239000003204 tranquilizing agent Substances 0.000 title claims abstract description 29
- 230000002936 tranquilizing effect Effects 0.000 title claims abstract description 29
- 239000000126 substance Substances 0.000 claims abstract description 50
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920000620 organic polymer Polymers 0.000 claims abstract description 21
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 230000003647 oxidation Effects 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011593 sulfur Substances 0.000 claims abstract description 8
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 7
- -1 polyethylene Polymers 0.000 claims description 15
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229920000098 polyolefin Polymers 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 229920001155 polypropylene Polymers 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 5
- 125000002592 cumenyl group Chemical group C1(=C(C=CC=C1)*)C(C)C 0.000 claims description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 11
- 238000001125 extrusion Methods 0.000 description 16
- 239000003963 antioxidant agent Substances 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 7
- 235000006708 antioxidants Nutrition 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- OKIRBHVFJGXOIS-UHFFFAOYSA-N 1,2-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=CC=C1C(C)C OKIRBHVFJGXOIS-UHFFFAOYSA-N 0.000 description 2
- UNEATYXSUBPPKP-UHFFFAOYSA-N 1,3-Diisopropylbenzene Chemical compound CC(C)C1=CC=CC(C(C)C)=C1 UNEATYXSUBPPKP-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 2
- GQJDFTIOKVGUOF-UHFFFAOYSA-N OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)C(CO)(CO)CO Chemical compound OP(O)OP(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)C(CO)(CO)CO GQJDFTIOKVGUOF-UHFFFAOYSA-N 0.000 description 2
- 230000004075 alteration Effects 0.000 description 2
- 229940069428 antacid Drugs 0.000 description 2
- 239000003159 antacid agent Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000005453 pelletization Methods 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- KHUXNRRPPZOJPT-UHFFFAOYSA-N phenoxy radical Chemical group O=C1C=C[CH]C=C1 KHUXNRRPPZOJPT-UHFFFAOYSA-N 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HVLLSGMXQDNUAL-UHFFFAOYSA-N triphenyl phosphite Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)OC1=CC=CC=C1 HVLLSGMXQDNUAL-UHFFFAOYSA-N 0.000 description 2
- 125000006671 (C6-C18) aromatic hydrocarbon group Chemical group 0.000 description 1
- ODJQKYXPKWQWNK-UHFFFAOYSA-L 3-(2-carboxylatoethylsulfanyl)propanoate Chemical compound [O-]C(=O)CCSCCC([O-])=O ODJQKYXPKWQWNK-UHFFFAOYSA-L 0.000 description 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical class [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BEIOEBMXPVYLRY-UHFFFAOYSA-N [4-[4-bis(2,4-ditert-butylphenoxy)phosphanylphenyl]phenyl]-bis(2,4-ditert-butylphenoxy)phosphane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(C=1C=CC(=CC=1)C=1C=CC(=CC=1)P(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C BEIOEBMXPVYLRY-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 230000000680 avirulence Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 229940000406 drug candidate Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000003777 experimental drug Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- KWUZCAVKPCRJPO-UHFFFAOYSA-N n-ethyl-4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical class C1=CC(NCC)=CC=C1C1=NC2=CC=C(C)C=C2S1 KWUZCAVKPCRJPO-UHFFFAOYSA-N 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000004781 supercooling Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- 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
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
-
- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
- C08K5/372—Sulfides, e.g. R-(S)x-R'
-
- 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
-
- 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
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- 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
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5393—Phosphonous compounds, e.g. R—P(OR')2
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A kind of combined type tranquilizer constituent, comprises a kind of phosphorous organic oxidation-resistant agent selected from least one in chemical formula 1 to chemical formula 8；And a kind of sulfur-containing carboxylate as shown in chemical formula 9, chemical formula 1 refers to claims and description to chemical formula 9.The present invention also provides for a kind of modified polymeric material, comprises an organic polymer base material and a kind of combined type tranquilizer constituent as above.Described combined type tranquilizer constituent is favorably improved the colour stability of organic polymer and processing stability so that modified polymeric material has good colour stability and processing stability.
Description
Technical field
The present invention relates to a kind of tranquilizer constituent, more particularly to one kind inclusion are phosphorous organic anti-
The combined type tranquilizer constituent of oxidant and sulfur-containing carboxylate compound, and through described combined type
The polymeric material of tranquilizer constituent modification.
Background technology
Existing organic polymer (such as polyolefin) has good chemical stability, machinery by force
Degree, electric insulating quality and product size stability, and there is avirulence and easy to process,
Thus be often widely used as thermoplastic engineering plastic.Though organic polymer has above-mentioned excellent
Point, but commercially available organic polymer heat energy effect under be oxidized easily degraded, cause xanthochromia with
And engineering propertiess decline.
Therefore, in order to prevent the oxidative degradation of organic polymer, add usually in extrusion processing procedure
Enter antioxidant to reduce the Degradation of organic polymer, to strengthen the machinery of organic polymer
Property and thermostability；However, antioxidant itself may lead to organic polymer colored and process
Stability declines.Additionally, typically antacid can be added in extrusion processing procedure, it is to suppress
Acidic materials cause organic polymer to degrade, however, the species of some antacids or addition
When more, organic polymer also can be led to colored and processing stability declines.
Content of the invention
The first object of the present invention is to provide a kind of combined type tranquilizer constituent, described compound
Formula tranquilizer constituent is used in the extrusion processing procedure of organic polymer, does not result in organic polymer
The problem that colored and processing stability declines.
Combined type tranquilizer constituent of the present invention comprises：
A kind of phosphorous organic oxidation-resistant agent selected from least one in chemical formula 1 to chemical formula 8；
And
A kind of sulfur-containing carboxylate as shown in chemical formula 9；
In chemical formula 1 to chemical formula 7, R11To R13、R21To R26、R31To R35、R41To R48、
R51To R56、R61To R64, and R71To R78Represent hydrogen, the tert-butyl group, cumenyl independently of one another
Or C1To C8Straight chained alkyl；T represents C1To C18Alkyl orR65To R67Each only
On the spot represent hydrogen, the tert-butyl group, cumenyl or C1To C8Straight chained alkyl；Z41、Z42、Z51And Z61
Represent O, S or C1To C4Stretch alkyl；
In chemical formula 9, Mq+Represent Ca2+、Mg2+、Zn2+Or Al3+, q represents that 2 or 3, t represent 0
To 6 integer, R91Represent hydrogen or C1To C18Alkyl, R92Represent C1To C30Alkyl, C6To C18Aromatic hydrocarbons
Base or R93OOC-(CH2)k-, wherein, R93Represent C1To C30Alkyl or C6To C18Aryl, k
Represent 1 to 5 integer.
Combined type tranquilizer constituent of the present invention, wherein, R in described chemical formula 991Represent hydrogen,
R92Represent C1To C12Alkyl, C6To C18Aryl or R93OOC-(CH2)k-, wherein, R93Represent
C1To C12Alkyl, k represents 1 or 2.
Combined type tranquilizer constituent of the present invention, wherein, R in described chemical formula 992Represent ten
Dialkyl group or H17C8OOCCH2-.
The second object of the present invention is to provide a kind of modified polymeric material, described through changing
The polymeric material of matter has good colour stability and processing stability.
The modified polymeric material of the present invention, comprises：A kind of organic polymer base material, and
A kind of combined type tranquilizer constituent as above.
The modified polymeric material of the present invention, wherein, described organic polymer base material is polyene
Hydrocarbon.
The modified polymeric material of the present invention, wherein, described polyolefin is selected from polyethylene
Or polypropylene.
The modified polymeric material of the present invention, wherein, with the weight of described organic polymer base material
Measure as 100 weight portions, the content range of described combined type tranquilizer constituent is 0.01 to 2.2 weight
Amount part.
The beneficial effects of the present invention is：Described combined type tranquilizer constituent passes through described phosphorous
Organic oxidation-resistant agent and sulfur-containing carboxylate, described combined type tranquilizer constituent has been favorably improved
The colour stability of machine polymer (particularly polyolefin) and processing stability.
Specific embodiment
Hereinafter will be described in detail with regard to present invention：
Phosphorous organic oxidation-resistant agent shown in described chemical formula 1 is such as, but not limited to：Three (2,4- bis-
The tert-butyl group) phenyl-phosphite (abbreviation antioxidant 168).Phosphorous shown in described chemical formula 2 has
Machine antioxidant is such as, but not limited to：Double (2,4- di-tert-butyl-phenyl) tetramethylolmethane diphosphorous acid
Double (2,4- diisopropylbenzene (DIPB) the phenoxyl) -2,4,8,10- of ester (abbreviation antioxidant 626), 3,9-
Four oxa- -3,9- two phospha spiral shell [5.5] hendecane (abbreviation antioxidant 9228).Described chemical formula
Phosphorous organic oxidation-resistant agent shown in 3 is such as, but not limited to：(cas number is 161717-32-4).Described chemical formula 4 institute
The phosphorous organic oxidation-resistant agent shown is such as, but not limited to：(cas number is
1601458-04-1).Phosphorous organic oxidation-resistant agent shown in described chemical formula 5 for example but does not limit
In：(cas number is 205518-79-2).Described chemical formula
Phosphorous organic oxidation-resistant agent shown in 6 is such as, but not limited to：2,4,8,10- tetra-tert
- 12H- diphenyl [d, g] [1,3,2] dioxy phospha eight ring is (referred to as -6- [(2- second hexyl) oxygen]
HP-10).
It is preferred that the R in described chemical formula 991Represent hydrogen, R92Represent C1To C12Alkyl, C6To C18
Aryl or R93OOC-(CH2)k-, wherein, R93Represent C1To C12Alkyl, k represents 1 or 2.On
The aryl stated refers to aryl, alkyl replaces aryl or the alkyl of aryl replacement.More preferably,
R in described chemical formula 992Represent dodecyl or H17C8OOCCH2-.
It is preferred that described organic polymer base material is polyolefin.More preferably, described polyolefin is
Selected from polyethylene or polypropylene.
It is preferred that with the weight of described organic polymer base material for 100 weight portions, described compound
The content range of formula tranquilizer constituent is 0.01 to 2.2 weight portion.
The present invention will be described further with regard to following examples, however, it should be noted that described reality
Apply example and only illustrate and be used, and be not necessarily to be construed as the restriction of present invention enforcement.
[experimental drug]
1. polypropylene：Hereinafter referred to as PP, purchased from Tai Hua company, the name of an article is B8001.
2. polyethylene：Hereinafter referred to as PE, purchased from Tai Hua company, the name of an article is LL120.
3. three (2,4- di-t-butyl) phenyl-phosphite：Phosphorous organic anti-shown in chemical formula 1
Oxidant, hereinafter referred to as 168.
4. pair (2,4- di-tert-butyl-phenyl) pentaerythritol diphosphites：Shown in chemical formula 2
Phosphorous organic oxidation-resistant agent, hereinafter referred to as antioxidant 626.
Double (2,4- diisopropylbenzene (DIPB) phenoxyl) -2,4,8,10- four oxa- -3,9- two phosphorus of 5.3,9-
Miscellaneous spiral shell [5.5] hendecane：Phosphorous organic oxidation-resistant agent shown in chemical formula 2, hereinafter referred to as anti-
Oxidant 9228.
6.Phosphorous organic antioxygen shown in chemical formula 3
Agent, hereinafter referred to as 161717-32-4.
7.For chemical formula 4
Shown phosphorous organic oxidation-resistant agent, hereinafter referred to as 1601458-04-1.
8.Phosphorous organic antioxygen shown in chemical formula 5
Agent, hereinafter referred to as 205518-79-2.
9.2,4,8,10- tetra-tert -6- [(2- second hexyl) oxygen] -12H- diphenyl
[d, g] [1,3,2] dioxy phospha eight ring：Phosphorous organic oxidation-resistant agent shown in chemical formula 6,
Hereinafter referred to as HP-10.
10.For
Phosphorous organic oxidation-resistant agent shown in chemical formula 7, hereinafter referred to as PEPQ.
11.9,10- dihydro-9-oxy miscellaneous -10- phospho hetero phenanthrene -10- oxide：Shown in chemical formula 8
Phosphorous organic oxidation-resistant agent, hereinafter referred to as DOPO.
12.[C12H25─S─CH2CH2COO]2Ca：Sulfur-containing carboxylate shown in chemical formula 9,
Hereinafter referred to as B1.
13.[C12H25─S─CH2CH2COO]3Al：Sulfur-containing carboxylate shown in chemical formula 9,
Hereinafter referred to as B2.
The double octadecyl ester of 14. thio-2 acids：The entitled disteaxyl of English
Thiodipropionate, hereinafter referred to as DSTDP.
＜ embodiment 1 to 15 ＞
According to the constituent shown in table 1 and ratio (weight portion), by 100 parts by weight of polypropylene or
100 weight account polyethylenes are uniformly mixed at 25 DEG C with combined type tranquilizer constituent, respectively
Polymeric material E1' to E15' to embodiment 1 to 15.
Table 1
＜ comparative example 1 to 16 ＞
According to the constituent shown in table 2 and ratio (weight portion), by 100 parts by weight of polypropylene or
100 weight account polyethylenes are uniformly mixed at 25 DEG C with tranquilizer constituent, respectively obtain and compare
The polymeric material CE1' to CE16' of example 1 to 16.
Table 2
Note：In table 1 and table 2, "-" represents no added.
Signature is mixed respectively with twin screw extruder (Taiwan Hong Yu Mechanology Inc. testing machine PSM20A)
Go out (temperature setting be 190 to 230 DEG C, screw speed be 200 revs/min, charging rate be 6 turns
/ minute) above-mentioned polymeric material E1' to E15' and CE1' to CE16', then through supercooling, air-dry,
Pelletizing, drying, prepare modified polymeric material E1 to E15 and CE1 to CE16 respectively.
Modified polymeric material E1 to E15 and CE1 to CE16 is repeated above-mentioned extrusion, cold
But, air-dry, pelletizing, drying steps.
[evaluation test]
1. yellow aberration (Δ b*Value)
Measured modified respectively using color difference meter (for the ColorQuest XE of HunterLab company)
Polymeric material E1 to E15 and CE1 to CE16 after the 3rd time and the 5th extrusion compared to the 1st
Value of chromatism (the Δ b of secondary extrusion*Value), result is as shown in table 3 and table 4.
2. melt index (melting index, MI) change (Δ MI)
Using laboratory fusion index instrument (the Laboratory Melt for Dynisco company
Indexer LMI D4004) point measurement modified polymeric material E1 to E15 and CE1 is extremely
CE16 melt index compared to the 1st extrusion after the 3rd time and the 5th extrusion changes Result is as shown in table 3 and table 4.
Table 3
Table 4
By table 3 and table 4 it is known that by embodiment 1 to 15 be obtained modified polymeric material
Material E1 to E15, the Δ b through the 3rd extrusion*Δ b below 2.66, through the 5th extrusion for the value*
Value is below 5.04.So, the modified polymeric material CE1 being obtained by comparative example 1 to 16 is extremely
CE16, the Δ b through the 3rd extrusion*Δ b more than 3.12, through the 5th extrusion for the value*It is worth 6.12
More than, display compared to the tranquilizer constituent of comparative example 1 to 16, embodiment 1 to 15 compound
Formula tranquilizer constituent makes modified polymeric material have relatively low yellow aberration (Δ b*
Value), represent that xanthochromia is less obvious, the colour stability for modified polymeric material has
Significantly benefit.
According to melt index change (Δ MI) result, by embodiment 1 to 15 be obtained modified
Polymeric material E1 to E15, the Δ MI through the 3rd extrusion below 161.58%, through the 5th
The Δ MI of extrusion is below 258.64%；So, the modified polymerization being obtained by comparative example 1 to 16
Thing material C E1 to CE16, the Δ MI through the 3rd extrusion more than 175.79%, through the 5th extrusion
Δ MI more than 314.41%, display is compared to the tranquilizer constituent of comparative example 1 to 16, real
The combined type tranquilizer constituent applying example 1 to 15 is able to maintain that adding of modified polymeric material
Apt qualitative (physical property).
In sum, combined type tranquilizer constituent of the present invention passes through described phosphorous organic oxidation-resistant
Agent and sulfur-containing carboxylate, for the colour stability improving organic polymer (particularly polyolefin)
And processing stability has significant synergism, described modified polymeric material can be made to have
There are good colour stability and processing stability, therefore really can reach the purpose of the present invention.
Be the above, be presently preferred embodiments of the present invention, when can not with this limit this
The scope that invention is implemented is that is to say, that generally according to claims of the present invention and description institute
The simple equivalence changes made and modification, all still belong in the range of the present invention covered.
Claims (7)
1. a kind of combined type tranquilizer constituent is it is characterised in that it comprises：
A kind of selected from the phosphorous organic oxidation-resistant of at least one in chemical formula 1 to chemical formula 8
Agent；And
A kind of sulfur-containing carboxylate as shown in chemical formula 9；
【Chemical formula 1】
【Chemical formula 2】
【Chemical formula 3】
【Chemical formula 4】
【Chemical formula 5】
【Chemical formula 6】
【Chemical formula 7】
【Chemical formula 8】
【Chemical formula 9】
In chemical formula 1 to chemical formula 7, R11To R13、R21To R26、R31To R35、R41To R48、
R51To R56、R61To R64, and R71To R78Represent hydrogen, the tert-butyl group, cumenyl independently of one another
Or C1To C8Straight chained alkyl；T represents C1To C18Alkyl orR65To R67Each only
On the spot represent hydrogen, the tert-butyl group, cumenyl or C1To C8Straight chained alkyl；Z41、Z42、Z51And
Z61Represent O, S or C1To C4Stretch alkyl；
In chemical formula 9, Mq+Represent Ca2+、Mg2+、Zn2+Or Al3+, q represents 2 or 3, t tables
Show 0 to 6 integer, R91Represent hydrogen or C1To C18Alkyl, R92Represent C1To C30Alkyl, C6Extremely
C18Aryl or R93OOC-(CH2)k-, wherein, R93Represent C1To C30Alkyl or C6To C18Virtue
Alkyl, k represents 1 to 5 integer.
2. combined type tranquilizer constituent as claimed in claim 1 it is characterised in that its,
R in described chemical formula 991Represent hydrogen, R92Represent C1To C12Alkyl, C6To C18Aryl or
R93OOC-(CH2)k-, wherein, R93Represent C1To C12Alkyl, k represents 1 or 2.
3. combined type tranquilizer constituent as claimed in claim 2 it is characterised in that its,
R in described chemical formula 992Represent dodecyl or H17C8OOCCH2-.
4. a kind of modified polymeric material is it is characterised in that it comprises：A kind of organic
Polymeric substrate, and a kind of combined type as claimed any one in claims 1 to 3 is stable
Agent constituent.
5. polymeric material modified as claimed in claim 4 it is characterised in that its,
Described organic polymer base material is polyolefin.
6. polymeric material modified as claimed in claim 5 it is characterised in that its,
Described polyolefin is selected from polyethylene or polypropylene.
7. polymeric material modified as claimed in claim 4 it is characterised in that its,
With the weight of described organic polymer base material for 100 weight portions, described combined type tranquilizer composition
The content range of thing is 0.01 to 2.2 weight portion.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3284779A1 (en) * | 2016-08-19 | 2018-02-21 | FDC, Lees Chemical Industry Co., Ltd. | Modified polymer composition and stabilizer mixture for making the same |
| CN109294151A (en) * | 2017-07-24 | 2019-02-01 | 奕益实业有限公司 | Modified polymer material and the mixture for being used to prepare polymer material |
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| DE1220602B (en) * | 1960-08-04 | 1966-07-07 | Bergwerksgesellschaft Hibernia | Process for stabilizing polyolefins |
| CN101003643A (en) * | 2006-12-30 | 2007-07-25 | 中国科学院广州化学研究所 | Composite stabilizer of metal salt of organic carboxylic acid containing sulfur in use for polymer containing halogen, and application |
| CN102432961A (en) * | 2011-11-16 | 2012-05-02 | 山东瑞丰高分子材料股份有限公司 | Composite heat stabilizer for polyvinyl chloride (PVC), and preparation method for composite heat stabilizer |
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| JPS53134049A (en) * | 1977-04-11 | 1978-11-22 | Sankyo Yuki Gosei Kk | Stabilization of synthetic resin |
| BRPI0504215A (en) * | 2004-10-08 | 2006-05-23 | Rohm & Haas | stabilized polymer composition, stabilizing composition, method for stabilizing a halogen containing vinyl polymer, and, article |
| CN102516684A (en) * | 2011-11-22 | 2012-06-27 | 山东瑞丰高分子材料股份有限公司 | Novel liquid calcium and zinc stabilizing agent and preparation method thereof |
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| DE1220602B (en) * | 1960-08-04 | 1966-07-07 | Bergwerksgesellschaft Hibernia | Process for stabilizing polyolefins |
| CN101003643A (en) * | 2006-12-30 | 2007-07-25 | 中国科学院广州化学研究所 | Composite stabilizer of metal salt of organic carboxylic acid containing sulfur in use for polymer containing halogen, and application |
| CN102432961A (en) * | 2011-11-16 | 2012-05-02 | 山东瑞丰高分子材料股份有限公司 | Composite heat stabilizer for polyvinyl chloride (PVC), and preparation method for composite heat stabilizer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3284779A1 (en) * | 2016-08-19 | 2018-02-21 | FDC, Lees Chemical Industry Co., Ltd. | Modified polymer composition and stabilizer mixture for making the same |
| CN109294151A (en) * | 2017-07-24 | 2019-02-01 | 奕益实业有限公司 | Modified polymer material and the mixture for being used to prepare polymer material |
| CN109294151B (en) * | 2017-07-24 | 2021-03-09 | 奕益实业股份有限公司 | Modified polymeric materials and mixtures for preparing polymeric materials |
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