CN116199843A - Polycarbodiimide compound and preparation method and application thereof - Google Patents

Polycarbodiimide compound and preparation method and application thereof Download PDF

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CN116199843A
CN116199843A CN202111461124.6A CN202111461124A CN116199843A CN 116199843 A CN116199843 A CN 116199843A CN 202111461124 A CN202111461124 A CN 202111461124A CN 116199843 A CN116199843 A CN 116199843A
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alkyl
arylene
substituted
polycarbodiimide compound
group
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唐晓峰
朱旭
张文彬
丁群
余子涯
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Shanghai Langyi Functional Materials Co ltd
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    • 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
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids

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  • Chemical Kinetics & Catalysis (AREA)
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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

The invention discloses a polycarbodiimide compound, a preparation method and application thereof. The structure of the polycarbodiimide compound is shown as a formula I. The polycarbodiimide compound has excellent thermal stability, and the further prepared polymer material has high ageing resistance and strong mechanical property;

Description

Polycarbodiimide compound and preparation method and application thereof
Technical Field
The invention relates to a polycarbodiimide compound, a preparation method and application thereof.
Background
Carbodiimide compounds have proven to be useful as excellent hydrolysis inhibitors for a range of materials including thermoplastic polyesters, polyester polyols, polyurethanes, polycarbonates, and nylons. The most obvious characteristic of the materials is that the molecular structures of the materials all contain ester bonds, and the existence of the ester bonds leads the materials to be easily broken by the ester bonds to form carboxyl terminal groups under the conditions of humidity or higher temperature. Further catalytic hydrolysis of the terminal carboxyl groups accelerates the breakage of the molecular chains, so that the service performance (such as mechanical performance) of the material is greatly reduced. The carbodiimide compound can eliminate residual acid and carboxyl end groups in the polymer, inhibit the occurrence of hydrolysis, greatly prolong the service life of the material and improve the service performance of the polymer material to a certain extent.
Currently, common carbodiimide-based compounds are largely classified into two major classes, monomeric and polymeric. Of these, monomeric carbodiimides such as the Stabaxol-1 type of the Rhin chemical Lebrain Co., ltd (RheinChemieRheinau GmbH) have the disadvantage of being volatile or thermally unstable, and they may release volatile toxic compounds, which greatly limits the environment in which they are used. The polymeric carbodiimide has the advantages of low volatility, good thermal stability and the like, and is widely applied to various fields, particularly the fields with higher requirements on processing temperature, such as PET, PC, PA, PA66 and other materials, and the processing temperature of the materials is high and mostly 210-300 ℃, so that the polycarbodiimide compound with high heat resistance is required to be selected as the hydrolysis resistance agent in the processing process so as to improve the service performance of the material. In general, the thermal degradation stability of a polymeric material has a positive correlation with its molecular weight, with the greater the molecular weight, the better the thermal stability and the less susceptible to degradation. The main synthesis methods of the polycarbodiimide compound comprise a bulk method and a solution method. The bulk method is a method for self-polymerizing one or more diisocyanate compounds in the presence of a catalyst, the viscosity of the system is continuously increased in the synthesis process, the system is difficult to stir in the later period of the reaction, the requirement on equipment is high, and the carbodiimide compound with high polymerization degree is difficult to obtain. For example, patent CN102504161A adopts a bulk method to synthesize the polycarbodiimide compound, and the molecular weight of the polycarbodiimide compound is 12000g/ml at maximum. The solution method is synthesized in the presence of a solvent, the reaction rate is slow, and most of the solution method has solvent residues, which is unfavorable for the later processing. For example, the patent CN107001245A adopts a combination of a bulk method and a solution method, and the molecular weight of the synthesized polycarbodiimide compound is less than 10000g/mol.
Therefore, the preparation method of the polycarbodiimide compound with high molecular weight and excellent heat resistance is a technical problem to be solved in the field.
Disclosure of Invention
The invention aims to overcome the defects of low molecular weight and poor thermal stability of a synthesized polycarbodiimide compound in the prior art, and provides the polycarbodiimide compound, and the preparation method and the application thereof.
One of the purposes of the invention is to provide a polycarbodiimide compound, wherein the structure of the polycarbodiimide compound is shown as a formula I:
Figure BDA0003385224140000021
wherein R is 1 is-L 1 -L 2 -L 3 -(L 1 To the left end of the group, L 3 To the right of the substituent, e.g. a fragment of formula I
Figure BDA0003385224140000022
Wherein L is 1 to-NCO, L 3 And->
Figure BDA0003385224140000023
A end of (a) is connected with the other end of (a);
L 1 is C 1-18 Alkylene group, C 6-10 Arylene of 1, 2, 3 or 4C 1-4 C substituted by alkyl 6-10 Arylene group of C 3-13 Or is C1, 2, 3 or 4 1-4 C substituted by alkyl 3-13 Is a cycloalkylene group of (2);
L 2 is C 1-4 Alkylene group, C 6-10 Arylene group of C 3-13 Or is absent (i.e. -L) 1 -L 2 -L 3 -is-L 1 -L 3 -)；
L 3 Is C 1-18 Alkylene group, C 6-10 Arylene of 1, 2, 3 or 4C 1-4 C substituted by alkyl 6-10 Or, in the absence (i.e. -L) 1 -L 2 -L 3 -is-L 1 -L 2 -)；
R 2 is-L 4 -L 5 -L 6 -(L 4 To the left end of the group, L 6 To the right of the substituent, e.g. a fragment of formula I
Figure BDA0003385224140000031
Wherein L is 4 Is connected with the c end, L 6 Connected with the d end);
L 4 is C 1-18 Alkylene group, C 3-13 Is C1, C2, C3 or C4 1-4 C substituted by alkyl 3-13 Cycloalkylene of C 6-10 Or, is 1, 2, 3 or 4C 1-4 C substituted by alkyl 6-10 Arylene of (a);
L 5 is C 1-4 Alkylene group, C 6-10 Arylene group of C 3-13 Or is absent (i.e. -L) 4 -L 4 -L 6 -is-L 4 -L 6 -)；
L 6 Is C 1-18 Alkylene group, C 6-10 Arylene of 1, 2, 3 or 4C 1-4 C substituted by alkyl 6-10 Or, in the absence (i.e. -L) 4 -L 5 -L 6 -is-L 4 -L 6 -、-L 4 -L 5 -or-L 4 -)；
n is 2-20;
m is 2-100;
the molecular weight of the polycarbodiimide compound shown in the formula I is 5-20 ten thousand.
In the present invention, L 1 In (C) 1-18 The alkylene group of (C) 1-6 Alkylene groups such as methylene,
Figure BDA0003385224140000032
Figure BDA0003385224140000033
In the present invention, L 1 In (C) 6-10 Arylene of (2) may be
Figure BDA0003385224140000034
In the present invention, L 1 In said quilt 1, 2, 3 or 4C' s 1-4 C substituted by alkyl 6-10 C in arylene group of (A) 6-10 Arylene of (2) may be
Figure BDA0003385224140000041
In the present invention, L 1 In said quilt 1, 2, 3 or 4C' s 1-4 C substituted by alkyl 6-10 C in arylene group of (A) 1-4 The alkyl group of (a) may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, for example methyl.
In the present invention, L 1 In (C) 3-13 The cycloalkylene group of (a) may be a cyclopropylene group, a cyclobutylene group, a cyclopentylene group or a cyclohexylene group, for example
Figure BDA0003385224140000042
Or->
Figure BDA0003385224140000043
In the present invention, L 1 In said quilt 1, 2, 3 or 4C' s 1-4 C substituted by alkyl 3-13 C in cycloalkylene group 3-13 The cycloalkylene group of (a) may be a cyclopropylene group, a cyclobutylene group, a cyclopentylene group or a cyclohexylene group, for example
Figure BDA0003385224140000044
Or->
Figure BDA0003385224140000045
In the present invention, L 1 In said quilt 1, 2, 3 or 4C' s 1-4 C substituted by alkyl 3-13 C in cycloalkylene group 1-4 The alkyl group of (a) may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, for example methyl.
In the present invention, L 2 In (C) 1-4 The alkylene group of (2) may be methylene,
Figure BDA0003385224140000046
Figure BDA0003385224140000047
Such as methylene.
In the present invention, L 2 In (C) 6-10 Arylene of (2) may be
Figure BDA0003385224140000048
In the present invention, L 2 In (C) 3-13 May be cycloalkylene group
Figure BDA0003385224140000049
In the present invention, L 3 In (C) 1-18 The alkylene group of (C) 1-6 Alkylene groups such as methylene,
Figure BDA0003385224140000051
Figure BDA0003385224140000052
In the present invention, L 3 In (C) 6-10 Arylene of (2) may be
Figure BDA0003385224140000053
In the present invention, L 3 In said quilt 1, 2, 3 or 4C' s 1-4 C substituted by alkyl 6-10 C in arylene group of (A) 6-10 Arylene of (2) may be
Figure BDA0003385224140000054
In the present invention, L 3 In said quilt 1, 2, 3 or 4C' s 1-4 C substituted by alkyl 6-10 C in arylene group of (A) 1-4 The alkyl group of (a) may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, for example methyl.
In one embodiment of the invention, -L 1 -L 2 -L 3 -is
Figure BDA0003385224140000055
Figure BDA0003385224140000056
Figure BDA0003385224140000057
More preferably +.>
Figure BDA0003385224140000058
In the present invention, L 4 In (C) 1-18 The alkylene group of (C) 1-6 Alkylene groups such as methylene,
Figure BDA0003385224140000059
Figure BDA00033852241400000510
In the present invention, L 4 In (C) 3-13 The cycloalkylene group of (a) may be a cyclopropylene group, a cyclobutylene group, a cyclopentylene group or a cyclohexylene group, for example
Figure BDA0003385224140000061
Or->
Figure BDA0003385224140000062
In the present invention, L 4 In said quilt 1, 2, 3 or 4C' s 1-4 C substituted by alkyl 3-13 C in cycloalkylene group 3-13 The cycloalkylene group of (a) may be a cyclopropylene group, a cyclobutylene group, a cyclopentylene group or a cyclohexylene group, for example
Figure BDA0003385224140000063
Or->
Figure BDA0003385224140000064
In the present invention, L 4 In said quilt 1, 2, 3 or 4C' s 1-4 C substituted by alkyl 3-13 C in cycloalkylene group 1-4 The alkyl group of (a) may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, for example methyl.
In the present invention, L 4 In (C) 6-10 Arylene of (2) may be
Figure BDA0003385224140000065
In the present invention, L 4 In said quilt 1, 2, 3 or 4C' s 1-4 C substituted by alkyl 6-10 C in arylene group of (A) 6-10 Arylene of (2) may be
Figure BDA0003385224140000066
In the present invention, L 4 In said quilt 1, 2, 3 or 4C' s 1-4 C substituted by alkyl 6-10 C in arylene group of (A) 1-4 The alkyl group of (a) may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, for example methyl or ethyl.
In the present invention, L 5 In (C) 1-4 The alkylene group of (2) may be methylene,
Figure BDA0003385224140000067
Figure BDA0003385224140000068
For example methylene or->
Figure BDA0003385224140000069
In the present invention, L 5 In (C) 6-10 Arylene of (2) may be
Figure BDA00033852241400000610
In the present invention, L 5 In (C) 3-13 May be cycloalkylene group
Figure BDA0003385224140000071
In the present invention, L 6 In (C) 1-18 The alkylene group of (C) 1-6 Alkylene groups such as methylene,
Figure BDA0003385224140000072
Figure BDA0003385224140000073
In the present invention, L 6 In the above, the C 6-10 Arylene of (2) may be
Figure BDA0003385224140000074
In the present invention, L 6 In said quilt 1, 2, 3 or 4C' s 1-4 C substituted by alkyl 6-10 C of arylene group of (2) 6-10 Arylene of (2) may be
Figure BDA0003385224140000075
In the present invention, L 6 In said quilt 1, 2, 3 or 4C' s 1-4 C substituted by alkyl 6-10 C in arylene group of (A) 1-4 The alkyl group of (a) may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or t-butylA group such as methyl or ethyl.
In one embodiment of the invention, -L 4 -L 5 -L 6 -is
Figure BDA0003385224140000076
Figure BDA0003385224140000077
Figure BDA0003385224140000081
More preferably
Figure BDA0003385224140000082
In the present invention, preferably, n=10 to 15; more preferably, n=10, 11 or 15.
In the present invention, preferably, m=10 to 50; more preferably, m=20, 25, 30 or 45.
In the present invention, the molecular weight of the compound represented by formula I is preferably 50000-140000g/mol, for example 50733g/mol, 61028g/mol, 112983g/mol or 138743g/mol.
In one embodiment of the present invention, the polycarbodiimide compound represented by formula I is any one of the following formulas A1 to A4:
Figure BDA0003385224140000083
Figure BDA0003385224140000091
another object of the present invention is to provide a method for preparing the polycarbodiimide compound, comprising the steps of:
(a) In the presence of a catalyst, diisocyanate shown as a formula II is subjected to a first polymerization reaction under the protection of nitrogen to obtain a compound shown as a formula III;
Figure BDA0003385224140000092
(b) Carrying out a second polymerization reaction on the compound shown in the formula III and diamine shown in the formula IV in the extrusion process of a double-screw extruder to obtain a polycarbodiimide compound shown in the formula I;
Figure BDA0003385224140000093
wherein R is 1 、R 2 The definitions of n and m are as described above.
In step (a), the catalyst may be conventional in the art, preferably comprises an organic phosphorus-based compound, a tertiary amine, a basic metal compound, an alkali metal or alkaline earth metal oxide, hydroxide, alkoxide, phenoxide, metal carboxylate, or a non-basic organometallic compound; more preferably, the organic phosphorus compound is included.
Wherein the organophosphorus compound may include 3-methyl-1-phenyl-2-phosphorus-1-oxide, 3-methyl-1-ethyl-2-phosphorus-1-oxide, 1, 3-dimethyl-2-phosphorus-1-oxide, 1-phenyl-2-phosphorus-1-oxide, or 1-ethyl-2-phosphorus-1-oxide.
The catalyst may be added in an amount of 50ppm to 9000ppm, preferably 1000ppm to 4000ppm; ppm refers to the mass concentration of the catalyst in terms of the mass of diisocyanate.
In step (a), the temperature of the reaction may be conventional in the art, preferably 140℃to 220 ℃.
The course of the reaction is generally followed by titration with di-n-butylamine toluene and the time to termination of the reaction is determined.
In general, the reaction is terminated when the content of isocyanate groups (NCO) is 2% to 4%; for example 2.51%, 2.9%, 3.63% or 3.85%; the percentage refers to the percentage of the mass of isocyanate groups to the mass of the compound represented by formula III.
Preferably, the reaction is terminated when the target degree of polymerization is reached, preferably from 10 to 15; for example 11.
In step (b), the twin screw extruder may be conventional in the art, wherein the twin screw aspect ratio may be 40:1 or 44:1 twin screws; the temperature control zone is preferably divided into a Q zone, q=6 to 8. The temperature control area is not too long, and the melt can generate yellowing due to long residence time; the temperature control zone is not too short, which can result in inadequate reaction of the melt and diamine.
More preferably, in the temperature control region, the temperature of the 1 st region is 100 to 120 ℃, the temperature of the Q region is 150 to 160 ℃, and the temperatures of the 2 nd region to the (Q-1) region are 150 to 220 ℃, respectively.
In step (b), the first material and the diamine are typically fed into the main feed port of a twin screw extruder via a metering pump.
The screw extrusion is typically followed by a step of cooling and pelletizing, as is conventional in the art.
The third object of the present invention is to provide an application of a polycarbodiimide compound shown in formula I as an anti-hydrolysis agent or stabilizer in amide polymers or ester polymers.
It is a fourth object of the present invention to provide a polymeric material comprising a polycarbodiimide compound as described above, and an amide-based polymer or an ester-based polymer;
wherein, when the polymer material includes the polycarbodiimide compound and the ester polymer as described above, the molecular weight of the ester polymer may be 10 ten thousand or more.
In the invention, the mass concentration of the polycarbodiimide compound can be 0.1-15%; preferably 0.5% -5%; more preferably 0.5% -2%; further preferably 1.0%; the percentage refers to the mass concentration of the mass of the polycarbodiimide compound to the mass of the amide-based polymer or ester-based polymer.
In the present invention, the amide-based polymer may be conventional in the art, such as nylon (PA 6 or PA 66).
The ester polymers may be one or more of polyurethanes, polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polytrimethylene terephthalate (PTT), polycarbonate (PC), polylactic acid (PLA) derivatives, polyhydroxyalkanoates (PHA) and polybutylene succinate (PBS), cyclohexanediol and terephthalic acid modified Polyesters (PCTA), thermoplastic polyester elastomers (TPEE), ethylene-vinyl acetate copolymers (EVA), and polybutylene terephthalate-adipate (PBAT), as is conventional in the art; preferably polyethylene terephthalate (PET), polybutylene terephthalate (PBT) or Polycarbonate (PC).
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that:
1. the polycarbodiimide compound has excellent thermal stability, is not easy to decompose in the processing process, has a high softening point, is in a particle shape, can be simply blended with plastic particles, and reduces the processing difficulty.
2. The polycarbodiimide compound has very good compatibility with materials, and is not easy to migrate in the use process.
3. The preparation method of the polycarbodiimide compound can realize the preparation of polymers with large molecular weight.
4. The polymer material containing the polycarbodiimide compound has high ageing resistance and strong mechanical property.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
In the following examples and comparative examples, the PA66 resin used was commercially available from henna, model EPR27;
the twin screw extruder used was commercially available from Corp. Plon (Nanj) mechanical Co., ltd., model number CTE35.
Example 1
(a) 50kg of diphenylmethane diisocyanate is accurately weighed and put into a 100L reaction kettle, 50g of 3-methyl-1-phenyl-2-phosphorus-1-oxide catalyst is added to react at 150 ℃ in nitrogen atmosphere, the reaction progress is titrated by di-n-butylamine toluene solution during the reaction, and the reaction is stopped when NCO% is 3.63, and the polymerization degree of the system is 10.0.
(b) Adding the melt into a double-screw extruder at a speed of 2kg/min through a metering pump, simultaneously adding p-phenylenediamine into the double-screw extruder at a speed of 89g/min through a metering pump, extruding and granulating through a screw to obtain polycarbodiimide compound particles A1, wherein the molecular weight of the A1 is 50733g/mol.
Wherein, the molecular formula of A1 is:
Figure BDA0003385224140000121
example 2
(a) 50kg of diphenylmethane diisocyanate is accurately weighed and put into a 100L reaction kettle, 60g of 3-methyl-1-phenyl-2-phosphorus-1-oxide catalyst is added to react under the nitrogen atmosphere at 160 ℃, the reaction progress is titrated by di-n-butylamine toluene solution during the reaction, and the reaction is stopped when NCO% is 2.51, and the polymerization degree of the system is 15.0.
(b) Adding the melt into a double-screw extruder at a speed of 2kg/min through a metering pump, simultaneously adding 4, 4-methylenebis (2, 6-diethyl) aniline into the double-screw extruder at a speed of 180g/min through the metering pump, and extruding and granulating through a screw to obtain polycarbodiimide compound particles A2, wherein the molecular weight of A2 is 112983g/mol.
Wherein, the molecular formula of A2 is:
Figure BDA0003385224140000131
example 3
(a) 50kg of isophorone diisocyanate is accurately weighed and put into a 100L reaction kettle, 250g of 3-methyl-1-phenyl-2-phosphorus-1-oxide catalyst is added to react at 180 ℃ in nitrogen atmosphere, the reaction progress is titrated by di-n-butylamine toluene solution during the reaction, and the reaction is stopped when NCO% is 3.85, and the polymerization degree of the system is 11.0.
(b) Adding the melt into a double-screw extruder at a speed of 2kg/min through a metering pump, simultaneously adding isophorone diamine into the double-screw extruder at a speed of 150g/min through the metering pump, extruding and granulating through a screw to obtain polycarbodiimide compound particles A3, wherein the molecular weight of A3 is 61028g/mol.
Wherein, the molecular formula of A3 is:
Figure BDA0003385224140000132
example 4
(a) 50kg of isophorone diisocyanate is accurately weighed and put into a 100L reaction kettle, 300g of 3-methyl-1-phenyl-2-phosphorus-1-oxide catalyst is added to react at 190 ℃ in nitrogen atmosphere, the reaction progress is titrated by di-n-butylamine toluene solution during the reaction, and the reaction is stopped when NCO% is 2.90, and the polymerization degree of the system is 15.0.
(b) Adding the melt into a double-screw extruder at a speed of 2kg/min through a metering pump, simultaneously adding isophorone diamine into the double-screw extruder at a speed of 82.5g/min through a metering pump, and extruding and granulating through a screw to obtain polycarbodiimide compound particles A4, wherein the molecular weight of A4 is 138743g/mol.
Wherein, the molecular formula of A4 is:
Figure BDA0003385224140000141
comparative example 1
50kg of diphenylmethane diisocyanate is accurately weighed and put into a 100L reaction kettle, 50g of 3-methyl-1-phenyl-2-phosphorus-1-oxide catalyst is added at 150 ℃ to react in nitrogen atmosphere, the reaction progress is titrated by di-n-butylamine toluene solution in the reaction process, and when NCO% is 3.63, the reaction is stopped, so that the polycarbodiimide compound B1 with the polymerization degree of 10.0 is obtained, and the molecular weight of B1 is 2313g/mol.
Wherein, the molecular formula of B1 is:
Figure BDA0003385224140000142
comparative example 2
50kg of isophorone diisocyanate is accurately weighed and put into a 100L reaction kettle, 300g of 3-methyl-1-phenyl-2-phosphorus-1-oxide catalyst is added at 190 ℃ to react in nitrogen atmosphere, the reaction progress is titrated by di-n-butylamine toluene solution in the reaction process, and when NCO% is 2.90, the reaction is stopped, so that a polycarbodiimide compound B2 with the polymerization degree of 15.0 is obtained, and the molecular weight of B2 is 2897g/mol.
Wherein, the molecular formula of B2 is:
Figure BDA0003385224140000143
comparative example 3
(a) 50kg of diphenylmethane diisocyanate is accurately weighed and put into a 100L reaction kettle, 50g of 3-methyl-1-phenyl-2-phosphorus-1-oxide catalyst is added to react at 150 ℃ in nitrogen atmosphere, the reaction progress is titrated by di-n-butylamine toluene solution during the reaction, and the reaction is stopped when NCO% is 3.63, and the polymerization degree of the system is 10.0.
(b) Adding the melt into a double-screw extruder at a speed of 2kg/min through a metering pump, extruding and granulating through a screw to obtain polycarbodiimide compound particles B3, wherein the molecular weight of the B3 is 2519g/mol.
Wherein, the molecular formula of B3 is:
Figure BDA0003385224140000151
comparative example 4
The polycarbodiimide compound (A1) obtained in example 1 was added to a liquid oil type low molecular weight substance (molecular weight < 10 ten thousand) at a mass ratio of 1.0%, and it was observed that the polycarbodiimide compound could not be dissolved in the liquid oil type low molecular weight substance, and thus could not be pelletized and injection molded to prepare a polymer material.
Effect example 1
In order to measure the molecular weight of the prepared polycarbodiimide compound, the preparation method is characterized by adopting an Ubbelohde viscosity method, and the testing method is as follows:
accurately weighing 0.125+/-0.005 g of sample (the polycarbodiimide compound prepared in the example or the comparative example) by using an FA2204B type electronic analytical balance, taking tetrachloroethane and phenol with a mass ratio of 1:1 as solvents, preparing 25ml of standard solution after the sample is fully dissolved, and testing the intrinsic viscosity [ eta ] of the sample by using a Ubbelohde viscometer with an inner diameter of 0.7-0.8 mm at a testing temperature of 25+/-0.1 ℃.
Figure BDA0003385224140000152
Wherein: [ eta ]]Is the intrinsic viscosity of the sample; c is the mass concentration of the sample solution; η (eta) sp To increase the specific viscosity (eta) sp ＝t/t 0 -1), t is the outflow time of the polymer solution, t 0 The run-off time for the pure solvents (tetrachloroethane and phenol).
The intrinsic viscosity test results of the polycarbodiimide compounds synthesized in examples 1 to 4 and comparative examples 1 to 2 are shown in the table below:
TABLE 1
Numbering device Intrinsic viscosity (dL/g)
Example 1 0.56
Example 2 0.83
Example 3 0.64
Example 4 0.92
Comparative example 1 0.21
Comparative example 2 0.23
Comparative example 3 0.22
From the intrinsic viscosity data, the preparation methods of examples 1 to 4 can produce polycarbodiimide compounds having an intrinsic viscosity of 0.56dL/g or more, and thus have a high molecular weight.
(II) in order to evaluate the application properties of the polycarbodiimide compounds of the present invention as an anti-hydrolysis agent and a stabilizer in PA66, the polycarbodiimide compounds synthesized in examples 1 to 4 and comparative examples 1 to 2 were added to PA66 at a mass ratio of 1.0%, pelletized, and injection molded to prepare dumbbell-shaped tensile bars, which were aged by boiling in a mixed solution of ethylene glycol and water at 110 ℃ (ethylene glycol: water mass ratio=1:1), and then tested for mechanical properties at different aging times (0 h, 48h, 96h, 120h, 168h, 192 h). The tensile strength of the bars with different aging times was tested by using a universal tensile machine, and the test results are shown in table 2.
TABLE 2
Figure BDA0003385224140000171
As can be seen from Table 2, the addition of the polycarbodiimide compounds of examples 1 to 4 as an anti-hydrolysis agent can significantly improve the mechanical properties during spline aging.
Wherein, the sample bars prepared by adopting the polycarbodiimide compounds in examples 1-4 still have tensile strength of more than 32Mpa when the aging time is 192 hours; the bars prepared from the polycarbodiimide compounds of comparative examples 1 to 3 had a tensile strength of 32MPa or less at 96 hours and even 19.5MPa or less at 192 hours, which was comparable to that of the blank PA 66.
It can be seen that the high molecular weight polycarbodiimide compounds of examples 1 to 4 were significantly better in hydrolysis resistance than the low molecular weight hydrolysis resistance.

Claims (10)

1. The polycarbodiimide compound is characterized in that the structure of the polycarbodiimide compound is shown as a formula I:
Figure FDA0003385224130000011
wherein R is 1 is-L 1 -L 2 -L 3 -；
L 1 Is C 1-18 Alkylene group, C 6-10 Arylene of 1, 2, 3 or 4C 1-4 C substituted by alkyl 6-10 Arylene group of C 3-13 Or is C1, 2, 3 or 4 1-4 C substituted by alkyl 3-13 Is a cycloalkylene group of (2);
L 2 is C 1-4 Alkylene group, C 6-10 Arylene group of C 3-13 Or is absent;
L 3 is C 1-18 Alkylene group, C 6-10 Arylene of 1, 2, 3 or 4C 1-4 C substituted by alkyl 6-10 Arylene of (a), or, is absent;
R 2 is-L 4 -L 5 -L 6 -；
L 4 Is C 1-18 Alkylene group, C 3-13 Is C1, C2, C3 or C4 1-4 C substituted by alkyl 3-13 Cycloalkylene of C 6-10 Or, is 1, 2, 3 or 4C 1-4 C substituted by alkyl 6-10 Arylene of (a);
L 5 is C 1-4 Alkylene group, C 6-10 Arylene group of C 3-13 Or is absent;
L 6 is C 1-18 Alkylene group, C 6-10 Arylene of 1, 2, 3 or 4C 1-4 C substituted by alkyl 6-10 Arylene of (a), or, is absent;
n is 2-20;
m is 2-100;
the molecular weight of the polycarbodiimide compound shown in the formula I is 5-20 ten thousand.
2. The polycarbodiimide compound according to claim 1, wherein said polycarbodiimide compound according to formula I satisfies one or more of the following conditions:
(1)L 1 in (C) 1-18 Alkylene of (C) 1-6 Alkylene groups such as methylene,
Figure FDA0003385224130000012
Figure FDA0003385224130000021
(2)L 1 In (C) 6-10 Is arylene of (2)
Figure FDA0003385224130000022
(3)L 1 In said quilt 1, 2, 3 or 4C' s 1-4 C substituted by alkyl 6-10 C in arylene group of (A) 6-10 Is arylene of (2)
Figure FDA0003385224130000023
(4)L 1 In said quilt 1, 2, 3 or 4C' s 1-4 C substituted by alkyl 6-10 C in arylene group of (A) 1-4 Alkyl of (2) is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, for example methyl;
(5)L 1 in (C) 3-13 Cycloalkyl radicals of (2) are cyclopropylene, cyclobutylene, cyclopentylene or cyclohexylene radicals, e.g
Figure FDA0003385224130000024
Or->
Figure FDA0003385224130000025
(6)L 1 In said quilt 1, 2, 3 or 4C' s 1-4 C substituted by alkyl 3-13 C in cycloalkylene group 3-13 Cycloalkyl radicals of (2) are cyclopropylene, cyclobutylene, cyclopentylene or cyclohexylene radicals, e.g
Figure FDA0003385224130000026
Or alternatively
Figure FDA0003385224130000027
(7)L 1 In said quilt 1, 2, 3 or 4C' s 1-4 C substituted by alkyl 3-13 C in cycloalkylene group 1-4 Alkyl of (2) is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, for example methyl;
(8)L 2 in (C) 1-4 Alkylene of (2) is methylene,
Figure FDA0003385224130000028
Figure FDA0003385224130000029
Such as methylene;
(9)L 2 in (C) 6-10 Is arylene of (2)
Figure FDA0003385224130000031
(10)L 2 In (C) 3-13 Is (1) cycloalkylene
Figure FDA0003385224130000032
(11)L 3 In (C) 1-18 Alkylene of (C) 1-6 Alkylene groups such as methylene,
Figure FDA0003385224130000033
Figure FDA0003385224130000034
(12)L 3 In (C) 6-10 Is arylene of (2)
Figure FDA0003385224130000035
(13)L 3 In said quilt 1, 2, 3 or 4C' s 1-4 C substituted by alkyl 6-10 C in arylene group of (A) 6-10 Is arylene of (2)
Figure FDA0003385224130000036
(14)L 3 In said quilt 1, 2, 3 or 4C' s 1-4 C substituted by alkyl 6-10 C in arylene group of (A) 1-4 Alkyl of (a) is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, for example methyl.
3. The polycarbodiimide compound according to claim 2, wherein said polycarbodiimide compound according to formula I satisfies one or more of the following conditions:
(1)L 4 in (C) 1-18 Alkylene of (C) 1-6 Alkylene groups such as methylene,
Figure FDA0003385224130000037
Figure FDA0003385224130000038
(2)L 4 In (C) 3-13 Cycloalkyl radicals of (2) are cyclopropylene, cyclobutylene, cyclopentylene or cyclohexylene radicals, e.g
Figure FDA0003385224130000041
Or->
Figure FDA0003385224130000042
(3)L 4 In said quilt 1, 2, 3 or 4C' s 1-4 C substituted by alkyl 3-13 C in cycloalkylene group 3-13 Cycloalkyl radicals of (2) are cyclopropylene, cyclobutylene, cyclopentylene or cyclohexylene radicals, e.g
Figure FDA0003385224130000043
Or alternatively
Figure FDA0003385224130000044
(4)L 4 In said quilt 1, 2, 3 or 4C' s 1-4 C substituted by alkyl 3-13 C in cycloalkylene group 1-4 Alkyl of (2) is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, for example methyl;
(5)L 4 in (C) 6-10 Is arylene of (2)
Figure FDA0003385224130000045
(6)L 4 In said quilt 1, 2, 3 or 4C' s 1-4 C substituted by alkyl 6-10 C in arylene group of (A) 6-10 Is arylene of (2)
Figure FDA0003385224130000046
(7)L 4 In said quilt 1, 2, 3 or 4C' s 1-4 C substituted by alkyl 6-10 C in arylene group of (A) 1-4 Alkyl of (2) is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, for example methyl or ethyl;
(8)L 5 in (C) 1-4 Alkylene of (2) is methylene,
Figure FDA0003385224130000047
Figure FDA0003385224130000048
For example methylene or->
Figure FDA0003385224130000049
/>
(9)L 5 In (C) 6-10 Is arylene of (2)
Figure FDA00033852241300000410
(10)L 5 In (C) 3-13 Is (1) cycloalkylene
Figure FDA0003385224130000051
(11)L 6 In (C) 1-18 Alkylene of (C) 1-6 Alkylene groups such as methylene,
Figure FDA0003385224130000052
Figure FDA0003385224130000053
(12)L 6 In the above, the C 6-10 Is arylene of (2)
Figure FDA0003385224130000054
(13)L 6 In said quilt 1, 2, 3 or 4C' s 1-4 C substituted by alkyl 6-10 C of arylene group of (2) 6-10 Is arylene of (2)
Figure FDA0003385224130000055
(14)L 6 In said quilt 1, 2, 3 or 4C' s 1-4 C substituted by alkyl 6-10 C in arylene group of (A) 1-4 The alkyl group of (a) is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl, for example methyl or ethyl.
4. The polycarbodiimide compound according to claim 1, wherein said polycarbodiimide compound according to formula I satisfies one or more of the following conditions:
(1)-L 1 -L 2 -L 3 -is
Figure FDA0003385224130000056
Figure FDA0003385224130000057
Figure FDA0003385224130000058
Preferably is
Figure FDA0003385224130000061
/>
(2)-L 4 -L 5 -L 6 -is
Figure FDA0003385224130000062
Figure FDA0003385224130000063
Figure FDA0003385224130000064
Preferably is
Figure FDA0003385224130000065
5. The polycarbodiimide compound according to claim 1, wherein said polycarbodiimide compound according to formula I satisfies one or more of the following conditions:
(1) n=10 to 15; preferably, n=10, 11 or 15;
(2) m=10 to 50; preferably, m=20, 25, 30 or 45;
(3) The molecular weight of the compound shown in the formula I is 50000-140000g/mol, such as 50733g/mol, 61028g/mol, 112983g/mol or 138743g/mol;
(4) The polycarbodiimide compound shown in the formula I is any one compound from the following formulas A1 to A4:
Figure FDA0003385224130000071
6. a method for producing a polycarbodiimide compound according to any one of claims 1 to 5, comprising the steps of:
(a) In the presence of a catalyst, diisocyanate shown as a formula II is subjected to a first polymerization reaction under the protection of nitrogen to obtain a compound shown as a formula III;
Figure FDA0003385224130000072
(b) Carrying out a second polymerization reaction on the compound shown in the formula III and diamine shown in the formula IV in the extrusion process of a double-screw extruder to obtain a polycarbodiimide compound shown in the formula I;
Figure FDA0003385224130000081
/>
wherein R is 1 、R 2 N and m are as defined in any one of claims 1 to 5.
7. The method for producing a polycarbodiimide compound according to claim 6, wherein said method for producing a polycarbodiimide compound satisfies one or more of the following conditions:
(1) In step (a), the catalyst comprises an organophosphorus compound, a tertiary amine, a basic metal compound, an alkali metal or alkaline earth metal oxide, hydroxide, alkoxide, phenoxide, metal carboxylate, or a non-basic organometallic compound; preferably comprising an organic phosphorus compound;
(2) In the step (a), the addition amount of the catalyst is 50ppm to 9000ppm, preferably 1000ppm to 4000ppm; ppm refers to the mass concentration of the catalyst to the mass of diisocyanate;
(3) In the step (a), the temperature of the reaction is 140-220 ℃;
(4) In the step (a), tracking the reaction process by adopting a di-n-butylamine toluene solution titration method, and determining the reaction termination time; preferably, the reaction is terminated when the target polymerization degree is reached, the target polymerization degree being 10 to 15; for example 11;
(5) In step (b), the twin screw aspect ratio is 40:1 or 44:1 twin screw;
(6) In the step (b), the temperature control area of the double screw is divided into a Q area, and Q=6-8;
preferably, in the temperature control zone, the temperature of the 1 st zone is 100-120 ℃, the temperature of the Q zone is 150-160 ℃, and the temperatures of the 2 nd zone to the (Q-1) zone are 150-220 ℃, respectively.
8. Use of a polycarbodiimide compound according to any one of claims 1 to 5 as an anti-hydrolysis agent or stabilizer in amide polymers or ester polymers.
9. A polymeric material comprising a polycarbodiimide compound according to any one of claims 1 to 5, and an amide polymer or an ester polymer;
wherein when the polymer material comprises the polycarbodiimide compound according to any one of claims 1 to 5 and an ester polymer, the molecular weight of the ester polymer is 10 ten thousand or more.
10. The polymeric material of claim 9, wherein the polymeric material satisfies one or more of the following conditions:
(1) The mass concentration of the polycarbodiimide compound is 0.1-15%; preferably 0.5% -5%; more preferably 0.5% -2%; further preferably 1.0%; the percentage refers to the mass concentration of the mass of the polycarbodiimide compound to the mass of the amide polymer or the ester polymer;
(2) The amide polymer is nylon;
(3) The ester polymer is one or more of polyurethane, polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, polycarbonate, polylactic acid derivatives, polyhydroxyalkanoates and polybutylene succinate, modified polyesters of cyclohexanediol and terephthalic acid, thermoplastic polyester elastomers, ethylene-vinyl acetate copolymers, and polybutylene terephthalate-adipate; preferably polyethylene terephthalate, polybutylene terephthalate or polycarbonate.
CN202111461124.6A 2021-11-30 2021-11-30 Polycarbodiimide compound and preparation method and application thereof Pending CN116199843A (en)

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