CN112745410A - Preparation method of in-situ crosslinked polyethylene with high thermal stability - Google Patents
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Abstract
The invention discloses a preparation method of in-situ crosslinked polyethylene with high thermal stability, which is characterized by comprising the following steps: 1) mixing methylaluminoxane, compound 1, [ (eta ] and5‑C5Me4)SiMe2(η1‑NCMe3)]TiCl2carrying out a first contact reaction with ethylene gas in toluene, quenching after the reaction is finished, and washing to obtain a polymer 1; 2) carrying out second contact reaction on the polymer 1, 3, 5-bis (tert-butyl) -4-hydroxybenzoic acid, 4-N, N-dimethylaminopyridine and the compound 2 in toluene to obtain a polymer 2; 3) the polymer 2 is subjected to in-situ crosslinking reaction at high temperature to obtain a polymer 3, namely the in-situ crosslinked polyethylene with high thermal stability. The polyethylene prepared by the method has good thermal oxidation resistance, the antioxidant is uniformly distributed in the resin and is not easy to exude,the antioxidant consumption is saved, and the heat resistance of the polyethylene is improved.
Description
Technical Field
The invention relates to preparation of polyethylene, in particular to a preparation method of in-situ crosslinked polyethylene with high thermal stability.
Background
Polyethylene (PE) is a thermoplastic resin made by the polymerization of ethylene (or ethylene with a small amount of a high carbon alpha-olefin). The synthetic process is simple, the cost is low, and the plastic is the cheapest and widely used plastic in the world. The polyethylene has the advantages of excellent low temperature resistance (the lowest use temperature can reach-100 ℃), good chemical stability, resistance to corrosion of most non-oxidative acids and alkalis, insolubility in common solvents at normal temperature, small water absorption, good electrical insulation and the like.
However, the melting temperature of the polyethylene resin is low, and the maximum use temperature does not exceed 100 ℃, thereby greatly limiting the application of the polyethylene resin in the high-temperature field. In addition, undoped polyethylene resin is easy to generate free radicals under high temperature or ultraviolet radiation, and molecular chains are crosslinked or branched due to free radical reaction, so that the physical properties of the undoped polyethylene resin are changed; meanwhile, the oxidation reaction induced by oxygen or other strong oxidants can lead to the breaking and degradation of molecular chains, and low molecular weight molecular chains containing polar groups, such as aldehyde, ketone, alcohol, acid, ester and the like, are generated, so that the properties of the resin are changed, and the strength is greatly reduced.
In the polyolefin industry, it is common practice to add a small amount of a Hindered Phenol (HP) antioxidant such as antioxidant 245 (diethylene glycol bis [ beta- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate ]), antioxidant 1067 (octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) -propionate), etc., immediately after polymerization, on the principle of terminating the radical reaction by the proton provided by the antioxidant and subsequent oxidation. Generally, commercial HP antioxidants are effective in the melt processing process, but for polyethylene resins, polar HP antioxidants are difficult to be uniformly mixed with highly-crystallized nonpolar high-density polyethylene (HDPE), and due to poor compatibility, HP antioxidant molecules are easily extruded to the surface of the resin by closely-packed and highly-crystallized polyethylene molecular chains, so that the antioxidant effect of the resin is weakened, the possibility that a human body directly contacts with antioxidant small molecules is increased, and health hazards are caused.
Disclosure of Invention
Aiming at the defects of the existing polyethylene or doped polyethylene and the preparation method thereof, the invention provides the preparation method of the in-situ crosslinked polyethylene with high thermal oxidation stability.
Therefore, the invention provides a preparation method of in-situ crosslinked polyethylene with high thermal stability, wherein the preparation method comprises the following steps:
1) mixing Methylaluminoxane (MAO), compound 1, [ (eta ] or5-C5Me4)SiMe2(η1-NCMe3)]TiCl2Carrying out a first contact reaction with ethylene gas in toluene, quenching after the reaction is finished, and washing to obtain a polymer 1;
2) carrying out second contact reaction on the polymer 1, 3, 5-bis (tert-butyl) -4-hydroxybenzoic acid (EDC), 4-N, N-Dimethylaminopyridine (DMAP) and the compound 2 in toluene to obtain a polymer 2;
3) the polymer 2 is subjected to in-situ crosslinking reaction at high temperature to obtain a polymer 3, namely in-situ crosslinked polyethylene with high thermal stability;
the reaction formula can be represented as follows:
wherein n is an integer of 1-9; r is-Me or-t-Bu.
In an embodiment of the present invention, the preparation method of the present invention more specifically includes:
1) under the condition of stirring, firstly adding methylaluminoxane and the compound 1 into a reaction kettle filled with a toluene solvent, then introducing ethylene gas, and then adding [ (eta ]5-C5Me4)SiMe2(η1-NCMe3)]TiCl2(metallocene), carrying out a first contact reaction, quenching after the reaction is finished, and washing to obtain a polymer 1;
2) adding polymer 1, 3, 5-bis (tert-butyl) -4-hydroxybenzoic acid and 4-N, N-dimethylaminopyridine into a reactor filled with a toluene solvent, then adding compound 2, and carrying out a second contact reaction to obtain polymer 2;
3) the polymer 2 is subjected to in-situ crosslinking reaction at high temperature to obtain the in-situ crosslinked polyethylene with high thermal stability.
In an embodiment of the present invention, step 1) may be performed in a high-pressure reaction tank equipped with a stirring device; preferably, in step 1), methylaluminoxane, compound 1 and [ (. eta.5-C)5Me4)SiMe2(η1-NCMe3)]TiCl2The mass ratio of (1): (1-6): (1-5). times.10-3。
In the present invention, the [ (eta 5-C) group5Me4)SiMe2(η1-NCMe3)]TiCl2Commercially available or prepared according to the prior art, reference being made to the prior art such as D.W.Carpentti, L.Kloppenburg, J.T.Kupec, J.L.Petersen, Application of amine ionization for the implementation of the electrophoretic preparation of electrophoretic and monomeric groups 4 compounds, accessing an appended amino function, structural characterization of [ (C5H4) SiMe2(N-t-Bu)]ZrCl2(NMe2H),Organometallics 15(1996)1572e1581。
In an embodiment of the present invention, the conditions of the first contact reaction include: the reaction temperature is 70-130 ℃, and the reaction time is 10-60 min; the reaction pressure is 0.5-3 MPa.
In an embodiment of the invention, in step 1), the quenching uses a methanolic solution of hydrogen chloride, the methanolic solution of hydrogen chloride (which may be expressed as methanol/hydrochloric acid) having a concentration of 0.5 mol/L; preferably, the [ (η)5-C5Me4)SiMe2(η1-NCMe3)]TiCl2Is added in the form of a toluene solution, [ (eta ] is5-C5Me4)SiMe2(η1-NCMe3)]TiCl2The concentration in toluene may be 2 mol/L. [ (eta.) of5-C5Me4)SiMe2(η1-NCMe3)]TiCl2The toluene solution (b) may be added to the reaction by injection, dropping, or the like.
In the embodiment of the present invention, the step 2) may be performed in an atmospheric pressure reactor, and in the step 2), the amount of the polymer 1, EDC, DMAP, and the compound 2 is 1: (0.2-1): (0.02-0.1): (0.1-0.6).
In an embodiment of the present invention, step 2) may be performed in an atmospheric pressure reactor, and the conditions of the second contact reaction include: the reaction temperature is 80-140 ℃, and the reaction time is 8-24 h.
In an embodiment of the invention, the second contact reaction is carried out in the presence of a protective gas. The protective gas is helium, argon or nitrogen.
In an embodiment of the present invention, in step 3), the high temperature condition includes: the reaction temperature is 140-190 ℃, and the reaction time is 12-48 h. In the step 3), under the condition of the invention, the polymer 2 can generate in-situ crosslinking reaction to obtain the in-situ crosslinked polyethylene with high thermal stability.
Compared with the prior art, the invention has the advantages that:
in the invention, hydroxyl is introduced into a polyethylene branched chain in polymerization, and is connected with a Hindered Phenol (HP) antioxidant fragment by a covalent bond (ester group), and the antioxidant fragment is in-situ bridged by a carbon-carbon double bond after further heating, thereby forming the crosslinked polyethylene resin. The antioxidant segments in the in-situ crosslinked polyethylene prepared by the method are uniformly distributed in the resin and are not easy to exude, meanwhile, the antioxidant consumption is saved, the thermal oxidation resistance is obviously improved, and on the other hand, the generated crosslinking greatly improves the heat resistance of the polyethylene resin (the use temperature is improved to more than 160 ℃ from 100 ℃).
Detailed Description
In order that the present invention may be more readily understood, the present invention will now be described in further detail by way of examples, which are given by way of illustration only and are not intended to limit the scope of the invention. The starting materials or components used in the present invention may be commercially or conventionally prepared unless otherwise specified.
Example 1
Preparation of in-situ crosslinked polyethylene with high thermal stability
1) 1L of toluene, 60mL of a toluene solution of Methylaluminoxane (MAO) (MAO mass fraction: 5%, density: 0.873g/mL,25 ℃ C.) and 12g of compound 1(n ═ 5) were put into an autoclave equipped with a stirrer, and ethylene gas was introduced thereinto to inject a solution containing 0.02mmol [ (. eta. ]. eta.5-C5Me4)SiMe2(η1-NCMe3)]TiCl2The solution was stirred at 110 ℃ and 1MPa for 30 min. Adding methanol/hydrochloric acid for quenching, separating precipitate, and washing with tetrahydrofuran to obtain polymer 1 (n-5);
2) adding 500mL of toluene, 10g of polymer 1 (N-5), 5g of 3, 5-bis (tert-butyl) -4-hydroxybenzoic acid (EDC) and 0.5g of 4-N, N-Dimethylaminopyridine (DMAP) into an atmospheric stirring reactor under the protection of argon, finally adding 3g of compound 2 (R-Me), fully reacting at the temperature of 110 ℃ for 12h, and cleaning to obtain polymer 2 (N-5, R-Me);
3) the polymer is subjected to in-situ crosslinking of the antioxidant fragment under high temperature conditions (reaction temperature 180 ℃, reaction time 24h) to form crosslinked polymer 3 (n-5, R-Me).
Example 2
Preparation of in-situ crosslinked polyethylene with high thermal stability
1) High pressure reaction to a stirred apparatus1L of toluene, 60mL of a toluene solution of Methylaluminoxane (MAO) (MAO mass fraction: 5%) and 24g of compound 1(n ═ 5) were added to the autoclave, and ethylene gas was introduced into the autoclave to inject 0.02mmol of a solution containing [ (. eta. ]5-C5Me4)SiMe2(η1-NCMe3)]TiCl2The solution was stirred at 110 ℃ and 1MPa for 30 min. Adding methanol/hydrochloric acid for quenching, separating precipitate, and washing with tetrahydrofuran to obtain polymer 1 (n-5);
step 2) and step 3) were the same as in example 1 to obtain polymer 3 (n-5, R-Me).
Example 3
Preparation of in-situ crosslinked polyethylene with high thermal stability
1) 1L of toluene, 60mL of a toluene solution of Methylaluminoxane (MAO) (MAO mass fraction: 5%) and 4g of compound 1(n ═ 5) were put into an autoclave equipped with a stirrer, and ethylene gas was introduced thereinto to inject 0.02mmol of a mixture containing [ (. eta. ]5-C5Me4)SiMe2(η1-NCMe3)]TiCl2The solution was stirred at 110 ℃ and 1MPa for 30 min. Adding methanol/hydrochloric acid for quenching, separating precipitate, and washing with tetrahydrofuran to obtain polymer 1 (n-5);
step 2) and step 3) were the same as in example 1 to obtain polymer 3 (n-5, R-Me).
Example 4
An in situ crosslinked polyethylene having high thermal stability was prepared as in example 1 except that compound 2(R ═ t-Bu) in step 2) to finally obtain polymer 3(n ═ 5, R ═ t-Bu).
Example 5
Preparation of in situ crosslinked polyethylene with high thermal stability as in example 1, except that the high temperature conditions in step 3) were: the reaction temperature was 140 ℃ and the reaction time was 12h, finally yielding polymer 3 (n-5, R-Me).
Example 6
Preparation of in situ crosslinked polyethylene with high thermal stability as in example 1, except that the high temperature conditions in step 3) were: the reaction temperature was 190 ℃ and the reaction was carried out for 48 hours, thus obtaining polymer 3 (n-5, R-Me).
Example 7
Preparation of in-situ crosslinked polyethylene with high thermal stability
1) 1L of toluene, 60mL of a toluene solution of Methylaluminoxane (MAO) (MAO mass fraction: 5%) and 12g of compound 1(n ═ 9) were put into an autoclave equipped with a stirrer, and ethylene gas was introduced into the autoclave to inject 0.02mmol of a solution containing [ (eta. ]5-C5Me4)SiMe2(η1-NCMe3)]TiCl2The solution was stirred at 110 ℃ and 1MPa for 30 min. Quenching with methanol/hydrochloric acid, separating the precipitate, and washing with tetrahydrofuran to obtain polymer 1 (n-9);
step 2) and step 3) were the same as in example 1 to obtain polymer 3(n ═ 9, R ═ Me).
Example 8
Preparation of in-situ crosslinked polyethylene with high thermal stability
1) 1L of toluene, 60mL of a toluene solution of Methylaluminoxane (MAO) (MAO mass fraction: 5%) and 12g of compound 1(n ═ 1) were put into an autoclave equipped with a stirrer, and ethylene gas was introduced into the autoclave to inject 0.02mmol of a solution containing [ (eta. ]5-C5Me4)SiMe2(η1-NCMe3)]TiCl2The solution was stirred at 110 ℃ and 1MPa for 30 min. Adding methanol/hydrochloric acid for quenching, separating precipitate, and washing with tetrahydrofuran to obtain polymer 1 (n-1);
step 2) and step 3) were the same as in example 1 to obtain polymer 3(n ═ 1, R ═ Me).
Example 9
An in situ crosslinked polyethylene having high thermal stability was prepared as in example 7, except that compound 2(R ═ t-Bu) in step 2) finally yielded polymer 3(n ═ 9, R ═ t-Bu).
Example 10
An in situ crosslinked polyethylene having high thermal stability was prepared as in example 8 except that compound 2(R ═ t-Bu) in step 2) to finally obtain polymer 3(n ═ 1, R ═ t-Bu).
Example 11
Preparation of in-situ crosslinked polyethylene with high thermal stability
1) 1L of toluene, 60mL of a toluene solution of Methylaluminoxane (MAO) (MAO mass fraction: 5%) and 12g of compound 1(n ═ 5) were put into an autoclave equipped with a stirrer, and ethylene gas was introduced into the autoclave to inject 0.02mmol of a solution containing [ (eta. ]5-C5Me4)SiMe2(η1-NCMe3)]TiCl2The toluene solution is stirred and reacted for 30min under the conditions of the temperature of 70 ℃ and the pressure of 0.5 MPa. Adding methanol/hydrochloric acid for quenching, separating precipitate, and washing with tetrahydrofuran to obtain polymer 1 (n-5);
step 2) and step 3) were performed in the same manner as in example 1 to obtain polymer 3(n ═ 5, R ═ t-Bu).
Example 12
Preparation of in-situ crosslinked polyethylene with high thermal stability
1) 1L of toluene, 60mL of a toluene solution of Methylaluminoxane (MAO) (MAO mass fraction: 5%) and 12g of compound 1(n ═ 5) were put into an autoclave equipped with a stirrer, and ethylene gas was introduced into the autoclave to inject 0.02mmol of a solution containing [ (eta. ]5-C5Me4)SiMe2(η1-NCMe3)]TiCl2The solution was stirred at 130 ℃ and 3MPa for 30 min. Adding methanol/hydrochloric acid for quenching, separating precipitate, and washing with tetrahydrofuran to obtain polymer 1 (n-5);
step 2) and step 3) were performed in the same manner as in example 1 to obtain polymer 3(n ═ 5, R ═ t-Bu).
Example 13
An in-situ crosslinked polyethylene having high thermal stability was prepared as in example 1, except that the reaction temperature of step 1) was 50 ℃, and polymer 3 (n-5, R-Me) was finally obtained.
Example 14
An in-situ crosslinked polyethylene having high thermal stability was prepared as in example 1 except that the reaction temperature of step 2) was 65 ℃, and polymer 3 (n-5, R-Me) was finally obtained.
Example 15
An in-situ crosslinked polyethylene having high thermal stability was prepared as in example 1, except that the reaction temperature of step 2) was 160 ℃, and polymer 3 (n-5, R-Me) was finally obtained.
Example 16
An in-situ crosslinked polyethylene having high thermal stability was prepared as in example 1, except that the reaction temperature of step 3) was 80 ℃, and polymer 3 (n-5, R-Me) was finally obtained.
Example 17
An in-situ crosslinked polyethylene having high thermal stability was prepared as in example 1, except that the reaction temperature of step 3) was 240 ℃, and polymer 3 (n-5, R-Me) was finally obtained.
The polymers 3 obtained in examples 1 to 17 were subjected to performance tests, and the specific results are shown in Table 1:
TABLE 1
Polymer 1 molecular weight Mv was determined by intrinsic viscosity of the polymer and dissolved in decalin solution at 135 c using a Cannon-ubpelohde viscometer. The polymer average molecular weight (Mv) was then calculated by the Mark-Houwink equation: [ eta ]]＝KMvαWherein K is 46 × 103And α is 0.73.
b Oxidative Induction Time (OIT) is the standard ASTM test method for examining antioxidant stabilization efficiency using DSC. Samples were tested at N according to ASTM D3895-14 procedure2Lower heat to raise the temperature. After reaching 190 ℃, the flow rate is changed into O at 50mL/min2The longer the enthalpy change begins to change significantly, the higher the thermal oxidative stability.
c gel content determination, polymer samples (in powder form) were treated with refluxing xylene for 24 hours to remove soluble fractions. The insoluble fraction was then dried in a vacuum oven at 65 ℃ overnight. Percent (%) gel content (%) - (W1-W2)/W1100% was calculated by the difference between the two weights before (W1) and after (W2) solvent extraction, and the gel content was positively correlated with the degree of crosslinking of the polymer.
The D Heat distortion temperature was measured using ASTM D648 test method.
In conclusion, the polyethylene prepared by the method has good thermal oxidation resistance, the antioxidant is uniformly distributed in the resin and is not easy to exude, the antioxidant consumption is saved, and the heat resistance of the polyethylene is improved.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A preparation method of in-situ crosslinked polyethylene with high thermal stability is characterized by comprising the following steps:
1) mixing methylaluminoxane, compound 1, [ (eta ] and5-C5Me4)SiMe2(η1-NCMe3)]TiCl2carrying out a first contact reaction with ethylene gas in toluene, quenching after the reaction is finished, and washing to obtain a polymer 1;
2) carrying out second contact reaction on the polymer 1, 3, 5-bis (tert-butyl) -4-hydroxybenzoic acid, 4-N, N-dimethylaminopyridine and the compound 2 in toluene to obtain a polymer 2;
3) the polymer 2 is subjected to in-situ crosslinking reaction at high temperature to obtain a polymer 3, namely in-situ crosslinked polyethylene with high thermal stability;
the reaction formula is shown as follows:
wherein n is an integer of 1-9; r is-Me or-t-Bu.
2. The method of claim 1, further comprising:
1) under the condition of stirring, firstly adding methylaluminoxane and the compound 1 into a reaction kettle filled with a toluene solvent, then introducing ethylene gas, and then adding [ (eta ]5-C5Me4)SiMe2(η1-NCMe3)]TiCl2Carrying out a first contact reaction, quenching after the reaction is finished, and washing to obtain a polymer 1;
2) adding polymer 1, 3, 5-bis (tert-butyl) -4-hydroxybenzoic acid and 4-N, N-dimethylaminopyridine into a reactor filled with a toluene solvent, then adding compound 2, and carrying out a second contact reaction to obtain polymer 2;
3) the polymer 2 is subjected to in-situ crosslinking reaction at high temperature to obtain the in-situ crosslinked polyethylene with high thermal stability.
3. The process according to claim 1 or 2, wherein in step 1), the methylaluminoxane, the compound 1 and [ (. eta. ] C5-C5Me4)SiMe2(η1-NCMe3)]TiCl2The mass ratio of (1): (1-6): (1-5). times.10-3。
4. The production method according to claim 1 or 2, wherein the conditions of the first contact reaction include: the reaction temperature is 70-130 ℃, and the reaction time is 10-60 min; the reaction pressure is 0.5-3 MPa.
5. According to claimThe production method according to 1 or 2, wherein in the step 1), the quenching uses a methanol solution of hydrogen chloride, and the concentration of the methanol solution of hydrogen chloride is 0.5 mol/L; the [ (eta ] of5-C5Me4)SiMe2(η1-NCMe3)]TiCl2Added as a toluene solution.
6. The method according to claim 1 or 2, wherein in step 2), the amount of polymer 1, EDC, DMAP, compound 2 is 1: (0.2-1): (0.02-0.1): (0.1-0.6).
7. The production method according to claim 1 or 2, wherein the conditions of the second contact reaction include: the reaction temperature is 80-140 ℃, and the reaction time is 8-24 h.
8. The production method according to claim 1 or 2, wherein the second contact reaction is carried out in the presence of a protective gas.
9. The method according to claim 1 or 2, wherein the protective gas is helium, argon, or nitrogen.
10. The production method according to claim 1 or 2, wherein in step 3), the high-temperature condition includes: the reaction temperature is 140-190 ℃, and the reaction time is 12-48 h.
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