CN109369440B - Preparation method of ethyl bismaleamic acid and complex thereof, method for repairing and degrading PVC and application - Google Patents

Preparation method of ethyl bismaleamic acid and complex thereof, method for repairing and degrading PVC and application Download PDF

Info

Publication number
CN109369440B
CN109369440B CN201811493979.5A CN201811493979A CN109369440B CN 109369440 B CN109369440 B CN 109369440B CN 201811493979 A CN201811493979 A CN 201811493979A CN 109369440 B CN109369440 B CN 109369440B
Authority
CN
China
Prior art keywords
pvc
ethyl
repairing
degraded
bismaleamic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811493979.5A
Other languages
Chinese (zh)
Other versions
CN109369440A (en
Inventor
李侃社
孙佳莹
康洁
李苗
牛红梅
陈创前
朱雪丹
章结兵
李锦�
汪晓芹
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian University of Science and Technology
Original Assignee
Xian University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xian University of Science and Technology filed Critical Xian University of Science and Technology
Priority to CN201811493979.5A priority Critical patent/CN109369440B/en
Publication of CN109369440A publication Critical patent/CN109369440A/en
Application granted granted Critical
Publication of CN109369440B publication Critical patent/CN109369440B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention relates to a preparation method of ethyl bismaleamic acid and a complex thereof, a method for repairing and degrading PVC and an application thereof, wherein the preparation process of the ethyl bismaleamic acid comprises the following steps of 1) weighing a certain amount of maleic anhydride and dissolving the maleic anhydride in acetonitrile to obtain a solution I; 2) weighing a certain amount of ethylenediamine, dissolving the ethylenediamine in acetonitrile to obtain a solution II, wherein the mass ratio of maleic anhydride to ethylenediamine is (1-3) to 1; 3) and dropwise adding the solution II into the solution I which is continuously stirred, fully reacting, performing suction filtration after the reaction is finished, washing, and drying a product obtained by suction filtration to constant weight to obtain the ethyl bismaleamic acid. The invention solves the technical problem that the degraded and aged PVC is lack of a repairing method, and provides an effective way for repairing the waste PVC products.

Description

Preparation method of ethyl bismaleamic acid and complex thereof, method for repairing and degrading PVC and application
Technical Field
The invention relates to the field of PVC repair, and particularly relates to a preparation method of ethyl bismaleamic acid and a complex thereof, a method for repairing and degrading PVC and application.
Background
Polyvinyl chloride (PVC) is a widely used material with many advantages such as high strength, corrosion resistance, and transparency. However, the thermal degradation during the processing process is inevitably affected by mechanical stress, pressure, heat, chemical reaction, electromagnetic radiation and the like during the use process, so that the polyvinyl chloride (PVC) material generates local damage and microcracks, and the microcracks can cause macrocracks to break, thereby affecting the normal use of the PVC material.
The prior art carries out stabilization modification on PVC. Zhu D Y et al successfully introduced nucleophilic thiol click chemistry based on the "thiol-ene" and "thiol-epoxy" reactions into commercial PVC with self-healing capabilities, healing processes were carried out in air at room temperature and took less time to achieve maximal healing compared to other self-healing thermoplastics of the external-aid type.
The development process of PVC has been hundreds of years, but the repair of degraded PVC is only rarely reported.
The evaluation of the self-healing effect of the polymer composite material can be represented by self-healing efficiency (eta) and is calculated according to the formula (1), namely the ratio of the mechanical property of the repaired sample to the mechanical property of the original sample:
Figure BDA0001896387880000011
disclosure of Invention
In order to solve the technical problem that degraded and aged PVC lacks a repair method, the invention provides a repair agent for repairing thermally degraded PVC, and provides a repair method by utilizing synthetic ethyl bismaleamic acid (H)2L) and the complex (CaL) thereof repair the degraded PVC with obvious effect.
The technical solution of the invention is as follows:
the invention provides a preparation method of ethyl bismaleamic acid, which is characterized by comprising the following steps:
1) weighing a certain amount of maleic anhydride, and dissolving in acetonitrile to obtain a solution I;
2) weighing a certain amount of ethylenediamine, dissolving the ethylenediamine in acetonitrile to obtain a solution II, wherein the mass ratio of maleic anhydride to ethylenediamine is (1-3) to 1;
3) and dropwise adding the solution II into the solution I which is continuously stirred, fully reacting, performing suction filtration after the reaction is finished, washing, and drying a product obtained by suction filtration to constant weight to obtain the ethyl bismaleamic acid.
Further: the mass ratio of maleic anhydride to ethylenediamine in step 2) is 2: 1.
the invention provides a method for repairing and degrading PVC by utilizing ethyl bismaleamic acid, which is characterized by comprising the following steps:
1) adding a repairing agent of ethyl bismaleamic acid to the degraded PVC; wherein the ethyl bismaleamic acid accounts for 2-10% of the mass of the degraded PVC;
2) and (4) mixing to obtain the repaired PVC.
Further, the step 2) is to set the temperature of the double-roll mixing mill to be 130-135 ℃ and the mixing time to be 10-15 min. The temperature of the front roller is higher than that of the rear roller, so that the roller is prevented from being stained.
Further, the repairing agent ethyl bismaleamic acid is four percent of the degraded PVC.
The invention provides an application of ethyl bismaleamic acid in repairing and degrading PVC (polyvinyl chloride)
The invention provides a preparation method of calcium ethyldimaleate, which is characterized by comprising the following steps:
1) preparation of Ethyl bismaleamic acid:
1.1) weighing a certain amount of maleic anhydride and dissolving in acetonitrile to obtain a solution I;
1.2) weighing ethylenediamine, and dissolving the ethylenediamine in acetonitrile to obtain a solution II; maleic anhydride and ethylenediamine are used in a mass ratio of 2: 1;
1.3) adding solution I dropwise to a continuously stirred solutionFully reacting in the solution II, filtering, washing and filtering after the reaction is finished, and drying a product obtained by filtering to constant weight to obtain the ethyl bismaleamic acid (H)2L)；
2) Preparation of calcium ethyldimaleate:
according to ethyl bismaleamic acid and Ca (OH)2The mass ratio of (1: 1) weighing a certain amount of Ca (OH)2And mixing and grinding for at least 30 minutes to obtain the calcium ethyl dimaleamide.
The invention provides a method for repairing and degrading PVC by utilizing calcium ethyldimaleate, which is characterized by comprising the following steps:
1) adding a repairing agent of calcium ethyl dimaleate to the degraded PVC; wherein the calcium ethyl dimaleate accounts for 2-10% of the mass of the degraded PVC;
2) and (3) mixing to obtain the repaired PVC, and setting the temperature of a double-roll mixer to be 130-135 ℃ and the mixing time to be 10-15 min.
Further, the repairing agent of calcium ethyl dimaleate is four percent of the mass of the degraded PVC.
The invention provides an application of ethyl dimaleate calcium to repair and degrade PVC.
The invention has the following beneficial effects:
1. the invention successfully synthesizes the ethyl bismaleamic acid (H) by a solvent method and solid-phase co-grinding2L) and the complex (CaL), the synthetic process is simple, a price-adjusting catalyst is not needed, and the method is environment-friendly.
2. The invention respectively converts H into2The L and the complex (CaL) thereof and the degraded PVC have Diels-Alder reaction to realize the restoration of the mechanical property of the degraded PVC, the reaction does not need to add a catalyst, the reaction condition is mild, and when H is used, the reaction is carried out2When the mass fraction of L is 4%, the tensile strength and the elongation at break repair rate respectively reach 109.8% and 150.3%, and the repair effect is obvious.
3. The ethyl bismaleamic acid repairs the degraded PVC, the repairing mechanism is realized by Diels-Alder reaction, the essence of the reaction is that diene reacts with dienophile to generate cyclohexene, and the thermal degradation of PVC is realized by using a click chemistry methodThe resulting conjugated dienes with synthetic H2And D-A reaction of dienophile in L to realize restoration.
4. The invention provides an effective way for repairing the waste PVC product.
Drawings
FIG. 1 Fourier transform infrared spectra of example 1 and example 2;
FIG. 2 is an infrared spectrum of degraded PVC and PVC repaired with H2L.
Detailed Description
Example 1: weighing 9g of maleic anhydride, and dissolving in acetonitrile to obtain a solution I; then weighing ethylenediamine and dissolving the ethylenediamine in acetonitrile according to the mass ratio of maleic anhydride to ethylenediamine of 2:1 to obtain a solution II; dropwise adding the solution II into the solution I which is continuously stirred, fully reacting, performing suction filtration after the reaction is finished, washing for 3 times by using deionized water, and drying a product obtained by suction filtration to constant weight to obtain the ethyl bismaleamic acid (H)2L)。
The content of C, H, N element in the product of example 1 was measured by an element analyzer, and the results are shown in Table 1. The synthesized ethyl bismaleamic acid is white powder, is insoluble in solvents such as ethanol and acetone, is easily soluble in N, N-dimethylformamide and has a molecular formula C10H12O6N2The relative molecular mass is 256.22, and the melting point is 194 +/-1 ℃.
Table 1 elemental content scale of the product of example 1
Figure BDA0001896387880000051
Example 2: weighing 9g of maleic anhydride, and dissolving in acetonitrile to obtain a solution I; then weighing ethylenediamine and dissolving the ethylenediamine in acetonitrile according to the mass ratio of maleic anhydride to ethylenediamine of 2:1 to obtain a solution II; dropwise adding the solution II into the solution I which is continuously stirred at a proper temperature, fully reacting, performing suction filtration after the reaction is finished, washing with deionized water for 3 times, and drying a product obtained by suction filtration to constant weight to obtain the ethyl bismaleamic acid (H)2L)。
According to ethyl bismaleamic acid and Ca(OH)2The amount ratio of the substances (A) to (B) is 1:1, Ca (OH) is weighed2And ethyl bismaleamic acid, mixed and ground for 30min to obtain calcium ethyl bismaleamic acid (CaL).
The products of examples 1 and 2 were each prepared as KBr pellets at 4000cm-1～400cm-1In the range of (1), a Nicolet corporation 170SXFT-IR type Fourier transform infrared spectrometer was used. The results are shown in FIG. 1.
Example 3: weighing 50g of PVC degraded for 90min in a constant-temperature oil bath at 200 ℃, then adding 2g of ethyl bismaleamic acid prepared in example 1, putting a fully and uniformly stirred PVC sample into a two-roll mixer for mixing and molding, setting the temperature of a front roller to be 135 ℃, the temperature of a rear roller to be 132 ℃, setting the temperature of the front roller to be higher than that of the rear roller before injection, preventing the rollers from being stained, setting the roller distance to be increased from 1 to 5 in an odd number, and mixing for 15 min.
The degraded PVC and the product of example 3 were each prepared as KBr pellets at 4000cm-1～400cm-1The results are shown in FIG. 2, using a Nicolet 170SXFT-IR type Fourier transform infrared spectrometer.
2976cm can be seen from the spectrogram 2-1、2903cm-1is-CH of a post-PVC-degrading aliphatic radical2A symmetric stretching vibration absorption peak and an anti-symmetric stretching vibration absorption peak. 1640cm in spectrum (a)-1The peak appears as a stretching vibration peak of conjugated C ═ C double bonds generated by degradation, and a plurality of disordered aromatic hydrocarbon absorption peaks. In spectrum (b), the PVC is degraded by H2After L repair, 1700cm can be seen-1H appears2C ═ O stretching vibration peak of L, 1567cm-1And 1494cm-1Respectively show H2The characteristic absorption peak of the C-N bond and the N-H bond of L is 1776cm-1There appears a characteristic absorption peak of the Diels-Alder reaction product, indicating that the Diels-Alder bond was successfully introduced into the degraded PVC chain, which is consistent with the reaction mechanism of Scheme 1.
Example 4: weighing 50g of PVC degraded for 90min in a constant-temperature oil bath at 200 ℃, then adding 2g of calcium ethyldimaleate prepared in example 2, putting the fully and uniformly stirred PVC sample into a two-roll mixer for mixing and molding, setting the temperature of a front roller to be 135 ℃, the temperature of a rear roller to be 132 ℃, setting the temperature of the front roller to be higher than that of the rear roller before injection, preventing the rollers from being stained, setting the roller distance to be increased from an odd number to 5, and mixing for 15 min.
And (3) comparison test:
pure PVC, PVC degraded for 90min, PVC repaired in example 3 and PVC repaired in example 4 are tested, the PVC is mixed and molded according to ASTM D3039/D3039-00 at the room temperature of 27 ℃ and the relative humidity of 38% RH, the testing of tensile property is carried out after the PVC is placed for 24h at the room temperature, the tensile speed is 20mm/min, at least five sample strips are measured in each group in the mechanical property testing, so that the accuracy is ensured, and the average value of the testing results is taken as the actual property of the material. The results of the experiment are shown in table 2:
table 2 is a table of the results of mechanical property tests on four materials
Figure BDA0001896387880000071
Examples 5 to 8
50g of PVC degraded for 90min in a constant-temperature oil bath at 200 ℃ is weighed, then 2%, 6%, 8% and 10% of the ethyl bismaleamic acid prepared in example 1 is respectively added in mass fraction, and the mixing parameters are the same as those in example 3.
Examples 5-8 were tested for mechanical properties of the repaired PVC. The results are shown in Table 3.
TABLE 3 comparative test with addition of plasticizer DOP
Figure BDA0001896387880000072
Examples 4 to 8 increase the plasticizer DOP during mixing. The content of the repairing agent has an important influence on the mechanical property repairing efficiency of the degraded PVC, and Table 3 shows that the repairing rate of the tensile strength and the elongation at break reaches the peak value when the adding mass fraction of the repairing agent is about 4%.
Example 9: DOP is added as a plasticizer, so that the change degree of tensile strength and elongation at break is inhibited, and multiple experiments prove thatThe realization of the reaction rule is not influenced. To further demonstrate the repairing effect, DOP was not added, repairing agent H2The mass fraction of L is 4%, the test results are shown in Table 4, the pure PVC has the tensile strength of 44.72MPa, and the tensile strength after degradation has little change, namely 41.8 MPa; degrading PVC and adding 4 percent of H by mass2The tensile strength after L reaches 49.1MPa, and the repair rate is 109.8 percent. The elongation at break of pure PVC is 29.59 percent, the plasticity is reduced due to the generation of conjugated polyene after degradation, the elongation at break is 21.21 percent, and the product is processed by H2L reaches 44.48 percent after being repaired, the repair rate is 150.3 percent, and the total repair rate is almost twice of that of pure PVC.
TABLE 4 comparative test without addition of plasticizer DOP
Figure BDA0001896387880000081
The reaction mechanism is as follows:
comparing PVC samples before and after degradation, finding that conjugated double bonds are generated by degradation, the tensile strength is increased, the brittleness is increased, and the elongation at break is obviously reduced; comparison H2The mechanical properties of the PVC sample before and after L repair show that the ethyl bismaleamic acid can be used as a repairing agent to improve the thermal stability and the initial-stage colorability resistance of PVC, the tensile strength of the degraded PVC is enhanced to a certain extent, and the original level can be repaired after the elongation at break is 24 hours; compared with the mechanical properties of the PVC sample before and after CaL restoration, CaL has certain restoration capability on the mechanical properties of the degraded PVC sample. H2The repair reaction mechanism of L on degraded PVC is as follows:
Figure BDA0001896387880000082
the degradation of conjugated diene structure contained in PVC and the D-A reaction of dienophile in ethyl bismaleamic acid to generate a ring stable structure, block the conjugated chain, improve the stability of the material and restore the mechanical property of PVC. The ethyl bismaleamic acid can be used as a heat stabilizer of PVC and a repairing agent for degrading PVC.

Claims (5)

1. A method for repairing and degrading PVC by utilizing ethyl bismaleamic acid is characterized in that:
1) adding a repairing agent of ethyl bismaleamic acid to the degraded PVC; wherein the ethyl bismaleamic acid accounts for 2-10% of the mass of the degraded PVC;
2) mixing to obtain repaired PVC; the temperature of the double-roller mixing machine is 130-135 ℃, and the mixing time is 10-15 min.
2. The method of claim 1 for the rehabilitation of degraded PVC by ethyl bismaleamic acid, characterized in that: the repairing agent ethyl bismaleamic acid is four percent of the mass of the degraded PVC.
3. A method for repairing and degrading PVC by utilizing calcium ethyldimaleate is characterized by comprising the following steps:
1) adding a repairing agent of calcium ethyl dimaleate to the degraded PVC; wherein the calcium ethyl dimaleate accounts for 2-10% of the mass of the degraded PVC;
2) and (3) mixing to obtain the repaired PVC, and setting the temperature of a double-roll mixer to be 130-135 ℃ and the mixing time to be 10-15 min.
4. The method for repairing degraded PVC using calcium ethyldimaleate according to claim 3, characterized in that:
the repairing agent of calcium ethyl dimaleate is four percent of the mass of the degraded PVC.
5. Application of calcium ethyldimaleate to repair and degrade PVC.
CN201811493979.5A 2018-12-07 2018-12-07 Preparation method of ethyl bismaleamic acid and complex thereof, method for repairing and degrading PVC and application Active CN109369440B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811493979.5A CN109369440B (en) 2018-12-07 2018-12-07 Preparation method of ethyl bismaleamic acid and complex thereof, method for repairing and degrading PVC and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811493979.5A CN109369440B (en) 2018-12-07 2018-12-07 Preparation method of ethyl bismaleamic acid and complex thereof, method for repairing and degrading PVC and application

Publications (2)

Publication Number Publication Date
CN109369440A CN109369440A (en) 2019-02-22
CN109369440B true CN109369440B (en) 2021-10-08

Family

ID=65372694

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811493979.5A Active CN109369440B (en) 2018-12-07 2018-12-07 Preparation method of ethyl bismaleamic acid and complex thereof, method for repairing and degrading PVC and application

Country Status (1)

Country Link
CN (1) CN109369440B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113603609B (en) * 2021-08-04 2022-07-12 西安交通大学 Polyvinyl chloride heat stabilizer and preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106046606A (en) * 2016-07-01 2016-10-26 西安科技大学 Maleamic acid-based calcium-zinc compound heat stabilizer as well as preparation method and application thereof

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106046606A (en) * 2016-07-01 2016-10-26 西安科技大学 Maleamic acid-based calcium-zinc compound heat stabilizer as well as preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
乙二胺双马来酰胺酸根合镧(Ⅲ) -层状矿物复合热稳定剂对聚氯乙烯的热稳定作用;李苗等;《高分子材料科学与工程》;20170531;第33卷(第5期);第109-117,123页 *
马来酸盐对聚氯乙烯热稳定性的影响;黎海霞等;《材料研究学报》;20121231;第26卷(第6期);第637-642页 *

Also Published As

Publication number Publication date
CN109369440A (en) 2019-02-22

Similar Documents

Publication Publication Date Title
Nun-anan et al. Novel approach to determine non-rubber content in Hevea brasiliensis: Influence of clone variation on properties of un-vulcanized natural rubber
CN110358099B (en) PVA-based composite material and precursor, remolded product, composite hydrogel, composite film, preparation and application thereof
CN109369440B (en) Preparation method of ethyl bismaleamic acid and complex thereof, method for repairing and degrading PVC and application
Daemi et al. A simple approach for morphology tailoring of alginate particles by manipulation ionic nature of polyurethanes
EP3015483A1 (en) Ethylene-vinylacetate-copolymers containing epoxy groups
CN114539486B (en) Polymer permanent antistatic agent and preparation method thereof
WO2021068443A1 (en) Preparation method for and application of tung oil-based polymer, and preparation method for tung oil-based polymer derivatives
Shan et al. Self-healing and malleable waterborne polyurethane bearing aliphatic disulfide linkages with hydrophobic branching chains
Wang et al. Mechanically robust, notch-insensitive, fatigue resistant and self-recoverable hydrogels with homogeneous and viscoelastic network constructed by a novel multifunctional cross-linker
CN116425766A (en) Epoxy isosorbide plasticizer and preparation method thereof
Zhao et al. Dissolution of cellulose in NaOH based solvents at low temperature
CN110294832A (en) A kind of polyurethane termoplastic elastomer and preparation method thereof of amino POSS modification
CN110337451B (en) Cellulose acetate, cellulose acetate composition, molded body, and film
CN110527159B (en) In-situ hydrogenated rubber graphene elastomer and preparation method thereof
Jin et al. Effects of molecular structure of acrylates on sizing performance of allyl grafted starch
CN112375308A (en) High-strength self-healing rubber material and preparation method thereof
CN112225829A (en) Polysaccharide with charged tail end and preparation method thereof
El-Nesr et al. Radiation synthesis and characterization of N, O-carboxymethyl chitosan/poly (vinylpyrrolidone) Copolymer Hydrogel
Chen et al. Facile preparation of near-monodisperse oligocellulose and its elastomeric derivatives with tunable mechanical properties
CN113956496A (en) Preparation method of novel two-dimensional nylon 6 antioxidant
Chen et al. Synthesis and Properties of Self-healing Metallopolymers with 5-Vinyltetrazole Units and Zn (II)
Zhang et al. Reed hemicellulose-based hydrogel prepared by glow discharge electrolysis plasma and its adsorption properties for heavy metal ions
Fang et al. Dual-functional photoinitiators and photo-grafting of cotton cellulose nanowhiskers
CN116515349B (en) Tara adhesive conductive coating and preparation method thereof
CN117327351B (en) Sealing ring rubber material for vehicle and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant