CN108192061A - A kind of random block type aromatic polycarbodiimide compound and preparation method thereof - Google Patents
A kind of random block type aromatic polycarbodiimide compound and preparation method thereof Download PDFInfo
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- CN108192061A CN108192061A CN201711416860.3A CN201711416860A CN108192061A CN 108192061 A CN108192061 A CN 108192061A CN 201711416860 A CN201711416860 A CN 201711416860A CN 108192061 A CN108192061 A CN 108192061A
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- Prior art keywords
- block type
- random block
- type aromatic
- polycarbodiimide compound
- aromatic polycarbodiimide
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- 125000003118 aryl group Chemical group 0.000 title claims abstract description 24
- 150000001875 compounds Chemical class 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 150000001718 carbodiimides Chemical class 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- -1 alkaline earth metal oxygen Compound Chemical class 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 6
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- 150000003141 primary amines Chemical group 0.000 claims description 3
- 150000003335 secondary amines Chemical class 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 150000002902 organometallic compounds Chemical class 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 claims description 2
- 229940031826 phenolate Drugs 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 10
- 229920000642 polymer Polymers 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000000203 mixture Substances 0.000 abstract description 4
- 230000003679 aging effect Effects 0.000 abstract description 2
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 abstract description 2
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 2
- 239000002932 luster Substances 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- 238000009833 condensation Methods 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 10
- 239000011574 phosphorus Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000004814 polyurethane Substances 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 102000054766 genetic haplotypes Human genes 0.000 description 3
- 239000004626 polylactic acid Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229920001427 mPEG Polymers 0.000 description 2
- 229920000747 poly(lactic acid) Polymers 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- YMAVXDRFOILNKI-UHFFFAOYSA-N 1-ethyl-2-isocyanato-3-methylbenzene Chemical class CCC1=CC=CC(C)=C1N=C=O YMAVXDRFOILNKI-UHFFFAOYSA-N 0.000 description 1
- KNHJIEOCVVIBIV-UHFFFAOYSA-N 2,3-dimethylphenyl isocyanate Chemical compound CC1=CC=CC(N=C=O)=C1C KNHJIEOCVVIBIV-UHFFFAOYSA-N 0.000 description 1
- FDSYTWVNUJTPMA-UHFFFAOYSA-N 2-[3,9-bis(carboxymethyl)-3,6,9,15-tetrazabicyclo[9.3.1]pentadeca-1(15),11,13-trien-6-yl]acetic acid Chemical compound C1N(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC2=CC=CC1=N2 FDSYTWVNUJTPMA-UHFFFAOYSA-N 0.000 description 1
- LLLVZDVNHNWSDS-UHFFFAOYSA-N 4-methylidene-3,5-dioxabicyclo[5.2.2]undeca-1(9),7,10-triene-2,6-dione Chemical compound C1(C2=CC=C(C(=O)OC(=C)O1)C=C2)=O LLLVZDVNHNWSDS-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000000655 anti-hydrolysis Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- PDXRQENMIVHKPI-UHFFFAOYSA-N cyclohexane-1,1-diol Chemical compound OC1(O)CCCCC1 PDXRQENMIVHKPI-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 239000005038 ethylene vinyl acetate Substances 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- MMHWNKSVQDCUDE-UHFFFAOYSA-N hexanedioic acid;terephthalic acid Chemical compound OC(=O)CCCCC(O)=O.OC(=O)C1=CC=C(C(O)=O)C=C1 MMHWNKSVQDCUDE-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- HNHVTXYLRVGMHD-UHFFFAOYSA-N n-butyl isocyanate Chemical compound CCCCN=C=O HNHVTXYLRVGMHD-UHFFFAOYSA-N 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001896 polybutyrate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920003225 polyurethane elastomer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
- C08G18/025—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only the polymeric products containing carbodiimide groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
By two kinds of aromatic diisocyanates condensation, end capping reaction occur for the present invention, synthesize a kind of random block type aromatic polycarbodiimide compound, structural formula is as follows：
Description
Technical field
The present invention relates to a kind of aromatic polycarbodiimide compounds and preparation method thereof more particularly to a kind of random embedding
Segment type aromatic polycarbodiimide compound and preparation method thereof.
Background technology
Carbodiimides have been proved to excellent anti-hydrolysis agent can be used as to be applied to thermoplastic, polynary
In a series of materials such as alcohol, polyurethane.This kind of material is most distinct feature is that all contain ester bond in molecular structure, the presence of ester bond
Lead to this kind of material at moist or higher temperature, the fracture of ester bond easily occurs, form end carboxyl.End carboxyl is further urged
Change hydrolysis and accelerate molecule chain break so that the performance of material is greatly reduced.And carbodiimides are deposited
Residual acid and end carboxyl in it can eliminate polymer inhibit the generation of hydrolysis, not only greatly extend the use of material
Service life, and the performance of polymer material is also improved to a certain extent.
At present, common carbodiimides are generally divided into haplotype carbodiimides and aggretion type carbonization two
Two major class of imines.Wherein, haplotype carbodiimides such as Rhein chemistry Lai Nao Co., Ltd (RheinChemieRheinau
GmbH Stabaxol-1 types), have the shortcomings that volatile or thermally labile, and they may release it is volatile
Toxic compounds, therefore it is unfavorable for it applied to high-temperature processing environment.The for another example carbon described in patent EP 0628541A1
Change diimine and must be based on specific raw material, it is expensive to obtain these raw materials, and product also has very high stick at room temperature
Degree, is unfavorable for addition in the product.The carbodiimides of aggretion type is single constitutional repeating unit according to report at present
Form, such as CN10250416A, polymer molecule backbone exist in the form of linear structure, have preferable crystal property, this is not
Conducive to the translucency of polymeric articles, it is limited using field particularly in the field more demanding to light transmission, is such as moulded
Expect the fields such as film, photovoltaic industry.For another example Rhein chemistry Lai Nao Co., Ltd (the RheinChemieRheinau of industrialization
GmbH Stabaxol-P type aggretion type carbodiimides), although molecular weight is larger, solves the disadvantage that haplotype is volatile,
It is not easy to extract out, small toxicity, but it uses single phenyl diisocyanate as raw material, single phenyl diisocyanate structure and methylene
The shortcomings of double phenyl diisocyanate structures are compared, and have that reactivity is high, polymerization product easy xanthochromia influences the appearance color of product
Pool, in material product particularly more demanding to color, such as in photovoltaic film, polyurethane shoe-sole material, xanthochromia
Problem seriously limits its application field.
Invention content
The present invention is intended to provide a kind of random block type aromatic polycarbodiimide compound, leads to following structure
Formula：
Wherein R1It is-NCN-R7Or-NHCONH-R8Or-NHCOOR9End group, R7、R8And R9To contain C1-C22Alkyl contains
There is C6-C12Cycloalkyl contains C7-C18Aralkyl, and R7、R8And R9Particularly preferably methyl, ethyl, isopropyl, tertiary fourth
Base, cycloalkyl, benzyl, 2,6- 3,5-dimethylphenyls, 2,6- diisopropyl phenyls, 2- methyl -6- ethylphenyls.
R2、R3And R4It is each independently methyl, ethyl, isopropyl, and R2、R3And R4Can only at most there be one of them
For methyl.
R5And R6It is each independently hydrogen, methyl, ethyl, isopropyl.
K, g=1-30, preferably 5-15；N=1-200, preferably 5-50.The random block type aromatic polycarbodiimide
The carbodiimide content (- N=C=N- contents, measured by oxalatimetry) by weight 8%~30% of object is closed, it is especially excellent
Selection of land by weight 10%~18%.
Invention further provides the methods for being used to prepare the random block type aromatic polycarbodiimide：
Aromatic diisocyanate (1) and aromatic diisocyanate (2) are at 100 DEG C~190 DEG C, catalyst, end-capping reagent
Condensation reaction and end capping reaction are carried out under the conditions of existing successively, obtains random block type aromatic polycarbodiimide chemical combination
Object.
Aromatic diisocyanate (1) and aromatic diisocyanate (2) molar ratio are 1:9~9:1.
The catalyst includes organophosphorus compound, tertiary amine, alkaline metal cpds, alkali or alkaline earth metal oxidation
Object, hydroxide, alcoholates or phenolate, metal carboxylate and non-alkaline organo-metallic compound, particularly preferred catalysis
Agent is organophosphorus compound.The additive amount of catalyst (feeds intake for 50ppm~9000ppm relative to aromatic diisocyanate
Weight), particularly preferably 1000ppm~4000ppm, wherein organophosphorus compound include 3- methyl-1s-phenyl -2- phosphorus -
1- oxides, 3- methyl-1s-ethyl -2- phosphorus -1- oxides, 1,3- dimethyl -2- phosphorus -1- oxides, 1- phenyl -2- phosphorus -1-
Oxide, 1- ethyl -2- phosphorus -1- oxides.
The end-capping reagent is primary amine, secondary amine, alcohol or monoisocyanates.Primary or secondary amine includes methylamine, ethamine and triethylamine etc.,
Wherein preferred ethamine；Alcohols includes methanol, ethyl alcohol, propyl alcohol, n-butanol, phenol, cyclohexanol, polyethylene glycol-methyl ether etc., wherein
It is preferred that cyclohexanol, polyethylene glycol-methyl ether；Monoisocyanates includes phenyl isocyanate, dimethylphenyl isocyanate, hexamethylene
Based isocyanate, butyl isocyanate etc., wherein it is preferred that phenyl isocyanate.
The addition mass concentration that polycarbodiimide in the present invention is applied in various base materials is 0.1%~15%, excellent
Selection of land 0.5%~10%, particularly preferably 0.5%~4%.
In the present invention, in the random block type polycarbodiimide formation of disordered structure reduce polycarbodiimide point
The crystallization degree of subchain structure, molecular backbone are initially formed netted physical crosslinking structure by opposite ordered structure so that mechanics
Performance ratio one-component is obviously improved, and optical property is also significantly improved, and transparency is improved, and is greatly improved
The color and luster of polymer product, it is easy to process.The random block polymer and single di-2-ethylhexylphosphine oxide that two kinds of monomers are formed simultaneously
The random block polymer phase ratio that phenyl diisocyanate is formed, can be by the degree of polymerization greatly under identical process conditions
It improves, the degree of polymerization further improves the thermal stability for increasing carbodiimides composition, particularly incipient degradation temperature；And
And as the raising of the degree of polymerization, the content of carbodiimide groups are accordingly promoted, this contributes to the promotion of hydrolytic Resistance, accordingly
Ageing properties can also get a promotion.
The random block type aromatic polycarbodiimide compound can be used as stabilisers against hydrolysis in following substance and production
It is applied in product：Polyalcohol, polyethylene terephthalate (PET), polybutylene terephthalate (PBT) based on ester, poly- pair
Phthalic acid propylene diester (PTT), copolyesters such as cyclohexanediol and terephthalic acid (TPA) modification polyester (PCTA), thermoplastic polyester
Elastomer (TPE E), ethylene vinyl acetate (EVA), polylactic acid (PLA) and/or PLA derivatives, polyhydroxy alkanoic acid ester
(PHA), poly terephthalic acid adipic acid fourth diester (PBAT), poly- succinic acid fourth diester (PBS), blend such as PA/PET or
PHA/PLA blends, triglycerides preferably trimethylolpropane tris oleate (TMP oleates), for lubricant industry
Oily preparation, thermoplastic polyurethane (TPU), polyurethane elastomer, PU adhesives, PU casting resins, PU foams or for timber,
The PU coating of leather, artificial leather and textile.
Specific embodiment
Following instance is for illustrating the present invention, but the present invention includes but not limited to specific embodiment.
Comparative example 1：
200g 2- methyl -4,6- diethylbenzenes group diisocyanate is added in the three-necked flask of 250ml and be passed through and continued
Nitrogen adds in after 100mg catalyst 3- methyl-1s-phenyl -2- phosphorus -1- oxides, system temperature is heated to 170 DEG C.Profit
With the tracking system NCO variations of di-n-butylamine titration until reaction system NCO content is 4.4%.Then pass through vacuum distillation
Mode removes the catalyst of system under the conditions of about 130 DEG C.Finally, temperature of reaction system is down to 120 DEG C of addition 7.8g ethamine
React away free NCO group.Obtained polycarbodiimide NCN contents are 18.9%, and polymerization degree n is about 9, and appearance is Huang
Color viscous melt.
Comparative example 2：
200g di-2-ethylhexylphosphine oxides (2- methyl -4- ethyls) phenyl isocyanate is added in the three-necked flask of 250ml and be passed through
Continuing nitrogen adds in after 100mg catalyst 3- methyl-1s-phenyl -2- phosphorus -1- oxides, system temperature is heated to 160
℃.Using the tracking system NCO variations of di-n-butylamine titration until reaction system NCO content is 2.8%.Then it is steamed by depressurizing
The mode evaporated removes the catalyst of system under the conditions of about 130 DEG C.Finally, temperature of reaction system is down to 80 DEG C and adds in 16g 2-
Methyl -6- ethylphenyl isocyanates reacts away free NCO group.Obtained polycarbodiimide NCN contents are
12.2%, polymerization degree n is about 9, melt color be light yellow solid, appearance substantial white powder after crushing.
Embodiment 1：
It is 1 by 200g molar ratios:2 2- methyl -4,6- diethylbenzenes group diisocyanates (0.22mol) and di-2-ethylhexylphosphine oxide
In the three-necked flask of (2- methyl -4- ethyls) phenyl isocyanate (0.44mol) addition 250ml and continuing nitrogen is passed through, is added in
After 100mg catalyst 3- methyl-1s-phenyl -2- phosphorus -1- oxides, system temperature is heated to 140 DEG C.Utilize di-n-butylamine
Titration tracking system NCO variations are until reaction system NCO content is 3.1%.Then about 130 by way of vacuum distillation
The catalyst of system is removed under the conditions of DEG C.Finally, by temperature of reaction system be down to 80 DEG C add in 6.3g ethanol synthesis fall it is free
NCO group.Obtained polycarbodiimide NCN contents are 13.6%, and polymerization degree n is about 9, and melt color is faint yellow intimate
Water white transparency solid, appearance is white powder after crushing.
Embodiment 2：
It is 1 by 200g molar ratios:1 2- methyl -4,6- diethylbenzenes group diisocyanates (0.35mol) and di-2-ethylhexylphosphine oxide
In the three-necked flask of (2- methyl -4- ethyls) phenyl isocyanate (0.35mol) addition 250ml and continuing nitrogen is passed through, is added in
After 100mg catalyst 3- methyl-1s-phenyl -2- phosphorus -1- oxides, system temperature is heated to 140 DEG C.Utilize di-n-butylamine
Titration tracking system NCO variations are until reaction system NCO content is 3.3%.Then about 130 by way of vacuum distillation
The catalyst of system is removed under the conditions of DEG C.Finally, by temperature of reaction system be down to 90 DEG C add in 8.7g isopropanol reactions fall it is free
NCO group.Obtained polycarbodiimide NCN contents are 14.2%, and polymerization degree n is about 9, and melt color is faint yellow near
Water white transparency solid, appearance is white powder after crushing.
Embodiment 3：
It is 2 by 200g molar ratios:1 2- methyl -4,6- diethylbenzenes group diisocyanates (0.50mol) and di-2-ethylhexylphosphine oxide
In the three-necked flask of (2- methyl -4- ethyls) phenyl isocyanate (0.25mol) addition 250ml and continuing nitrogen is passed through, is added in
After 100mg catalyst 3- methyl-1s-phenyl -2- phosphorus -1- oxides, system temperature is heated to 140 DEG C.Utilize di-n-butylamine
Titration tracking system NCO variations are until reaction system NCO content is 3.7%.Then about 130 by way of vacuum distillation
The catalyst of system is removed under the conditions of DEG C.Finally, by temperature of reaction system be down to 70 DEG C add in 5.0g methanol react away it is free
NCO group.Obtained polycarbodiimide NCN contents are 16.2%, and polymerization degree n is about 9, and melt color is faint yellow intimate
Water white transparency solid, appearance is white powder after crushing.
In order to assess in the present invention random block type polycarbodiimide class compound as stabilisers against hydrolysis at poly- pair
Application performance in ethylene terephthalate (PET).Implementation example is as follows：
By polycarbodiimide class compound synthesized in embodiment 1,2,3,4,5 and comparative example 1 with 0.5% ratio
Add in polyethylene terephthalate (PET), prepare dumbbell shaped tensile bars, batten 120 DEG C, 101MPa, saturation
It is tested in ageing oven under the conditions of water vapour, then tests the mechanical performance of each batten.Using tensilon to difference
The batten of ageing time carries out tensile strength test, and test result is as shown in table 1.
As seen from the table, for blank PET after aging 2 days, tensile strength drops to 1MPa, and mechanical performance substantially reduces；Comparison
For example 1 and 2 after aging 10 days, tensile strength drops to 10MPa or so, compares, the polycarbodiimide of addition this patent synthesis
For the Examples 1 to 3 of class compound after aging 6 days, tensile strength still maintains 30MPa or so, and anti-aging property carries significantly
It rises.
1 anti-aging property of table is tested
Claims (9)
1. a kind of random block type aromatic polycarbodiimide compound, it is characterised in that：Have the following structure general formula：
Wherein R1It is-NCN-R7Or-NHCONH-R8Or-NHCOOR9End group, R7、R8And R9To contain C1-C22Alkyl contains C6-
C12Cycloalkyl contains C7-C18Aralkyl；R2、R3And R4It is each independently methyl, ethyl, isopropyl, and R2、R3And R4
It is methyl that can only at most have one of them；R5And R6It is each independently hydrogen, methyl, ethyl, isopropyl；K, g=1-30, n=1-
200。
2. a kind of method for preparing random block type aromatic polycarbodiimide compound described in claim 1, feature
It is：At 100 DEG C~190 DEG C, catalyst, end-capping reagent exist for aromatic diisocyanate (1) and aromatic diisocyanate (2)
Under conditions of carry out condensation reaction and end capping reaction successively, obtain random block type aromatic polycarbodiimide compound, change
It is as follows to learn reaction equation：
3. a kind of random block type aromatic polycarbodiimide compound according to claim 1, it is characterised in that：K,
G=5-15, n=5-50.
4. a kind of random block type aromatic polycarbodiimide compound according to claim 1, it is characterised in that：R7、
R8And R9For methyl, ethyl, isopropyl, tertiary butyl, cycloalkyl, benzyl, 2,6- 3,5-dimethylphenyls, 2,6- diisopropyl phenyls,
2- methyl -6- ethylphenyls.
5. a kind of random block type aromatic polycarbodiimide compound according to claim 1, it is characterised in that：It should
The carbodiimide content by weight 8%~30% of random block type aromatic polycarbodiimide compound.
6. a kind of method for preparing random block type aromatic polycarbodiimide compound according to claim 2,
It is characterized in that：Aromatic diisocyanate (1) and aromatic diisocyanate (2) molar ratio are 1:9~9:1.
7. a kind of method for preparing random block type aromatic polycarbodiimide compound according to claim 2,
It is characterized in that：The catalyst includes organophosphorus compound, tertiary amine, alkaline metal cpds, alkali or alkaline earth metal oxygen
Compound, hydroxide, alcoholates or phenolate, metal carboxylate and non-alkaline organo-metallic compound.
8. a kind of method for preparing random block type aromatic polycarbodiimide compound according to claim 2,
It is characterized in that：The end-capping reagent is primary amine, secondary amine, alcohol or monoisocyanates.
9. a kind of method for preparing random block type aromatic polycarbodiimide compound according to claim 1,
It is characterized in that：The random block type aromatic polycarbodiimide compound be applied to various base materials in addition mass ratio be
0.1%~15%.
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| CN115850694A (en) * | 2022-12-29 | 2023-03-28 | 上海朗亿功能材料有限公司 | Polymeric carbodiimide compound hydrolysis-resistant agent and preparation method and application thereof |
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