CN110563916B - PPC resin derivative and online preparation method thereof - Google Patents

PPC resin derivative and online preparation method thereof Download PDF

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Publication number
CN110563916B
CN110563916B CN201911017692.XA CN201911017692A CN110563916B CN 110563916 B CN110563916 B CN 110563916B CN 201911017692 A CN201911017692 A CN 201911017692A CN 110563916 B CN110563916 B CN 110563916B
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polyol
mixture
resin derivative
parts
diol
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CN110563916A (en
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徐坤
徐玉华
林建新
何程林
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Jiangsu Zhongke Jinlong Environmental Protective New Materials Co ltd
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Jiangsu Zhongke Jinlong Environmental Protective New Materials Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/02—Making granules by dividing preformed material
    • B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
    • B29B9/065—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion under-water, e.g. underwater pelletizers
    • 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
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • 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
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
    • 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
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/4208—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups
    • C08G18/4211—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols
    • C08G18/4213—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing aromatic groups derived from aromatic dicarboxylic acids and dialcohols from terephthalic acid and dialcohols
    • 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
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • 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
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • 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
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4833—Polyethers containing oxyethylene units
    • 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
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6611—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • 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
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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    • 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
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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    • C08G2230/00—Compositions for preparing biodegradable polymers
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
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    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/06—Polyurethanes from polyesters

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to the technical field of PPC (polypropylene random copolymer) resin, in particular to a PPC resin derivative and an online preparation method thereof, wherein the PPC resin derivative comprises the following raw materials in parts by weight: 100 parts of polyol, 15-60 parts of isocyanate, 2.4-17 parts of micromolecular diol and 0.1-0.2 part of catalyst, wherein the polyol is a mixture of polycarbonate polyol and other polyols, the other polyols are at least one of polycaprolactone polyol, other polyester polyol, sorbitol and organic silicon polyol, and the molar ratio of the polycarbonate polyol to the other polyols is 12-15: 1. The invention has the advantages of excellent biodegradation performance, high thermal stability and high mechanical performance.

Description

PPC resin derivative and online preparation method thereof
Technical Field
The invention relates to the technical field of PPC (polypropylene random copolymer) resin, in particular to a PPC resin derivative and an online preparation method thereof.
Background
The development of socio-economic has led to an increasing demand for fossil fuels by humans, resulting in carbon dioxide (CO)2) The discharge amount of (b) tends to increase. As is well known, CO2Is one of the main gases causing the greenhouse effect, and the global warming brings very serious consequences, such as the subsidence of glaciers, the rise of sea level, desertification and the like, and directly threatens the survival of the human society. Meanwhile, with the continuous improvement of the living standard of human beings, the consumption of plastic products is increased day by day. While the plastic brings convenience to the life of people, a large amount of used plastic waste is increased continuously, a large amount of non-degradable plastic waste causes white pollution, and a non-negligible negative effect is caused to the natural environment which we rely on to live.
Heddle in situWhen two problems of greenhouse effect and white pollution are examined, the people find that CO2And propylene oxide under the action of a catalyst to generate polymethyl ethylene carbonate (PPC) through copolymerization. PPC can be completely biodegraded, can partially replace the traditional general plastic for use, and is helpful for solving the problem of white pollution caused by the traditional petroleum-based plastic. By using CO2In the synthesis of PPC as a raw material, CO can be used2The greenhouse effect is relieved, and the dependence of plastics on petroleum resources is reduced; on the other hand, a fully biodegradable material can be obtained if the CO discharged by industrial production can be treated2The PPC is prepared into degradable PPC and widely used, which can relieve the greenhouse effect to a certain extent and is beneficial to reducing white pollution.
The PPC serving as a novel aliphatic polyester has good degradation performance and barrier property, and has the advantages of transparency, no toxicity and the like, so that the PPC has a good application prospect in the aspects of food packaging, medical materials, adhesives, engineering plastics and the like. The PPC has asymmetric molecular chain structure and good flexibility, belongs to completely amorphous plastics, has the glass transition temperature of about 35 ℃, small tensile strength (3-30MPa and closely related to the test temperature), extremely high elongation at break (more than 700 percent), strong deformation recovery after stretching and strong temperature sensitivity of the tensile strength. However, the melt processing temperature of PPC is above 100 ℃, thermal degradation occurs near 170 ℃, thermal stability is poor, and the mechanical properties of PPC are relatively poor.
Chinese patent application CN1426430A discloses thermoplastic polyurethane elastomers (TPUs) prepared with polypropylene carbonate soft segments comprising: a) poly (trimethylene carbonate) glycol (PTMC glycol) as a soft segment; b) a diisocyanate; and c) at least one diol which reacts with the diisocyanate to form a hard segment in an amount of 10 to 55% by weight of the composition, wherein the hard segment is defined as the sum of the diisocyanate reacted with the diol and the unreacted diol moieties. The elastomers are somewhat harder than corresponding TPUs based on polyols well known in the art. The PTMC TPUs had good physical and mechanical properties, including a slightly higher modulus of elasticity than the reference TPU. The abrasion resistance and compression set are also very good compared to polyether TPUs, and the softening temperature and the coefficient of thermal expansion are also improved compared to reference TPUs. In addition, by using PTMC polyols, the transparency of TPUs can be increased and even completely transparent materials can be obtained. However, the heat stability and mechanical properties of the polyurethane elastomer prepared from PTMC polyol are still to be further improved.
Chinese patent application CN109694494A discloses a biodegradable thermoplastic polyurethane elastomer foaming bead and a preparation method thereof, belonging to the technical field of polymers. The polyurethane elastomer foaming bead is composed of the following substances in parts by mass: 100 portions and 200 portions of bio-based polyol; 20-100 parts of isocyanate; 10-100 parts of a micromolecular alcohol chain extender; 0.1-10 parts of ultraviolet absorbent; 0.1-10 parts of a catalyst; 1-20 parts of a physical foaming agent; wherein the bio-based polyol is a combination of two or more of poly (methyl ethylene carbonate) diol (PPC), polycaprolactone diol (PCL), polylactic acid (PLA) or Polyglycolide (PGA). The prepared foaming bead can be rapidly degraded while ensuring the original foaming multiplying power, strength and density, and can be widely applied to industries such as packaging and the like. Meanwhile, the patent application also provides a preparation method of the compound, which is scientific, reasonable, simple and feasible. But the biodegradability of the expanded beads is to be further improved.
Therefore, it is necessary to develop a PPC resin derivative and an on-line preparation method thereof, which can solve the above-mentioned technical problems.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a PPC resin derivative with excellent biodegradability, high thermal stability and high mechanical property and an online preparation method thereof.
The invention is realized by the following technical scheme:
the PPC resin derivative comprises the following raw materials in parts by weight: 100 parts of polyol, 15-60 parts of isocyanate, 2.4-17 parts of micromolecular diol and 0.1-0.2 part of catalyst, wherein the polyol is a mixture of polycarbonate polyol and other polyols, the other polyols are at least one of polycaprolactone polyol, other polyester polyol, sorbitol and organic silicon polyol, and the molar ratio of the polycarbonate polyol to the other polyols is 12-15: 1.
By limiting the weight parts of the raw materials of the PPC resin derivative and the molar ratio of different alcohols in the polyhydric alcohol, the finally prepared PPC resin derivative not only has flexibility, but also has rigidity, and the mechanical property is obviously improved.
Preferably, the polycarbonate polyol is polypropylene carbonate polyol or a mixture of polyethylene carbonate polyol and polypropylene carbonate polyol.
More preferably, the molecular weight of the polypropylene carbonate polyol is 1500-4000 and the functionality is 2-6.
More preferably, the mass ratio of the polyethylene carbonate polyol to the polypropylene carbonate polyol is 1: 4-6.
Preferably, the other polyester polyol is at least one of polyethylene glycol adipate glycol, 1, 4-butanediol adipate glycol, polyethylene glycol sebacate glycol and polyethylene glycol phthalate glycol.
Preferably, the other polyester polyol is at least one of polyethylene adipate glycol and poly (phthalic acid) glycol.
Preferably, the silicone polyol is an organosiloxane diol.
Preferably, the polyol is one of a combination of polycarbonate polyol and polycaprolactone polyol, polycarbonate polyol and other polyester polyols, polycarbonate polyol and sorbitol, polycarbonate polyol and silicone polyol, polycarbonate polyol, polycaprolactone polyol and other polyester polyols, polycarbonate polyol, other polyester polyols and sorbitol, polycarbonate polyol, other polyester polyols and silicone polyol, polycarbonate polyol, polycaprolactone polyol, other polyester polyols and sorbitol, polycaprolactone polyol, other polyester polyols, sorbitol and silicone polyol.
More preferably, the other polyol is a mixture of other polyester polyol and sorbitol.
More preferably, the mass ratio of the other polyester polyol to sorbitol is 2-3: 1.
Preferably, the isocyanate is at least one of 4,4 '-diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate.
More preferably, the isocyanate is at least one of 4, 4' -diphenylmethane diisocyanate, toluene diisocyanate, and isophorone diisocyanate.
Preferably, the small molecular diol is at least one of ethylene glycol, 1, 4-butanediol, propylene glycol, 1, 4-cyclohexanediol and neopentyl glycol.
More preferably, the small molecule diol is at least one of 1, 4-butanediol, propylene glycol and 1, 4-cyclohexanediol.
More preferably, the small molecule diol is a mixture of 1, 4-butanediol, propylene glycol, 1, 4-cyclohexanediol.
More preferably, the mass ratio of the 1, 4-butanediol to the propylene glycol to the 1, 4-cyclohexanediol is 2-4:1: 0.5-2.
Preferably, the catalyst includes at least one of tin-based, bismuth-based, and butyl titanate.
More preferably, the tin includes at least one of stannous octoate, stannous isooctoate, tributyl methoxy tin, t-butoxy tin, phenoxy tin, stannic chloride, stannic bromide, and acetylated tin.
More preferably, the bismuth group includes at least one of bismuth nitrate and bismuth naphthenate.
The invention also relates to a preparation method of the PPC resin derivative, which comprises the following steps:
(1) mixing polyalcohol, isocyanate, micromolecular diol and a catalyst to obtain a mixture A;
(2) and injecting the mixture A into a feed inlet of a double-screw extruder, extruding, granulating under water, and drying to obtain the composite material.
Preferably, the step (1) includes the steps of: heating the polyalcohol, the isocyanate, the micromolecular diol and the catalyst to 50-80 ℃ at the same time, and mixing to obtain a mixture A.
Preferably, the step (2) includes the steps of: and injecting the mixture A into a feed inlet of a double-screw extruder through a casting machine, reacting for 1.5-3 minutes at the temperature of 360mm multiplied by 15 sections and 1-7 sections of 130-170 ℃ and the temperature of 8-15 sections of 150-200 ℃, and granulating and drying under water at the temperature of 30-60 ℃ to obtain the compound A. The section 1 is closest to the feed inlet.
The double-screw extruder is a 95-type double-screw extruder, the diameter of a screw is 93.4mm, and the length-diameter ratio is 60: 1.
More preferably, the PPC resin derivative is prepared by a method comprising the steps of:
(1) simultaneously heating polyol, isocyanate, micromolecular diol and a catalyst to 50-80 ℃, and mixing to obtain a mixture A;
(2) and injecting the mixture A into a feed inlet of a double-screw extruder through a casting machine, reacting for 1.5-3 minutes at the temperature of 360mm multiplied by 15 sections and 1-7 sections of 130-170 ℃ and the temperature of 8-15 sections of 150-200 ℃, and granulating and drying under water at the temperature of 30-60 ℃ to obtain the compound A.
Preferably, the PPC resin derivative further comprises 20-40 parts of polyethylene glycol.
The invention also relates to a preparation method of the PPC resin derivative, which comprises the following steps:
(1) mixing polyalcohol, isocyanate, micromolecular diol and a catalyst to obtain a mixture A;
(2) and injecting the mixture A into a feed inlet of a double-screw extruder, adding polyethylene glycol, extruding, granulating under water, and drying to obtain the composite material.
Preferably, the preparation method of the PPC resin derivative comprises the steps of:
(1) simultaneously heating polyol, isocyanate, micromolecular diol and a catalyst to 50-80 ℃, and mixing to obtain a mixture A;
(2) and injecting the mixture A into a feed inlet of a double-screw extruder through a casting machine, wherein the temperature of 360mm multiplied by 15 sections is 130-.
The invention has the beneficial effects that:
according to the invention, by limiting the weight parts of the raw materials of the PPC resin derivative and the molar ratio of the polycarbonate polyol to other polyols in the polyol, the finally prepared PPC resin derivative not only has flexibility, but also has rigidity, and the degradation performance and the mechanical property are obviously improved.
When polycarbonate polyol, other polyester polyol and sorbitol are used together as polyol, the proportion of different polyols is limited, and the mechanical property of the finally prepared PPC resin derivative is obviously improved.
According to the invention, specific polyhydric alcohol, isocyanate, micromolecular diol and catalyst are selected, the component ratio of each component is limited, especially the micromolecular diol is limited to be a mixture of 1, 4-butanediol, propylene glycol and 1, 4-cyclohexanediol, the molecular weight of the finally prepared PC resin derivative can reach more than 10 ten thousands, the high temperature resistance can reach more than 120 ℃, namely, the PC resin derivative is still not adhered at the temperature, and the mechanical property and the biodegradation property of the product are improved.
According to the invention, by adding polyethylene glycol, the internal structure of the particles is optimized, and the mechanical property and the biodegradation property of the product are improved.
The PPC resin derivative is prepared by a one-step method, a solvent is not required to be added in the preparation process, the preparation is simple, the cost and the energy consumption are low, the processing performance is excellent, and harmful gases are not discharged in the preparation process.
In the preparation process, the mechanical property and the biodegradation property of the PPC resin derivative prepared by limiting the reaction temperatures of different charging barrels before and after the preparation, namely the temperature of 1-7 sections is 130-150 ℃, and the temperature of 8-15 sections is 150-200 ℃.
The thin film prepared by using the PPC resin derivative prepared by the invention as a raw material has excellent elongation at break and tear strength, has high barrier property to oxygen and water vapor, can realize complete biodegradation by composting, has special properties such as good compatibility with other biodegradable materials, and can be widely applied to industries such as packaging, mulching films, disposable articles and the like.
Detailed Description
The invention will be further described with reference to specific embodiments, and the advantages and features of the invention will become apparent as the description proceeds. These examples are illustrative only and do not limit the scope of the present invention in any way. It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.
The twin-screw extruder of the present invention is a 95 type twin-screw extruder, unless otherwise specified, and has a screw diameter of 93.4mm and a length-to-diameter ratio of 60: 1.
Example 1
The PPC resin derivative comprises the following raw materials in parts by weight: 100 parts of polyol, 15 parts of 4, 4' -diphenylmethane diisocyanate, 2.4 parts of micromolecular diol and 0.1 part of stannous octoate, wherein the polyol is a mixture of polypropylene carbonate dihydric alcohol (with the molecular weight of 1500) and polycaprolactone dihydric alcohol (with the molar ratio of 12: 1).
The small molecular diol is a mixture of 1, 4-butanediol, propylene glycol and 1, 4-cyclohexanediol, and the mass ratio of the small molecular diol to the propylene glycol to the 1, 4-cyclohexanediol is 2:1: 0.5.
A method for preparing PPC resin derivatives, comprising the steps of:
(1) simultaneously heating polyol, 4' -diphenylmethane diisocyanate, micromolecular diol and stannous octoate to 50 ℃, and mixing to obtain a mixture A;
(2) and (3) injecting the mixture A into a feed inlet of a double-screw extruder through a casting machine, reacting at the temperature of 360mm multiplied by 15 sections, 1-7 sections at 130 ℃ and 8-15 sections at 150 ℃ for 1.5 minutes, extruding, granulating under water at 30 ℃, and drying to obtain the compound A.
Example 2
A PPC resin derivative is different from the PPC resin derivative in example 2 only in that the other polyol is a mixture of polyethylene glycol adipate and sorbitol in a mass ratio of 2:1, and the rest conditions are the same.
Example 3
The PPC resin derivative comprises the following raw materials in parts by weight: 100 parts of polyol, 60 parts of toluene diisocyanate, 17 parts of small molecular diol and 0.2 part of bismuth nitrate, wherein the polyol is a mixture of polycarbonate polyol and other polyol (the molar ratio is 15: 1).
The polycarbonate polyol is a mixture of polyethylene carbonate dihydric alcohol (with a molecular weight of 4000) and polypropylene carbonate dihydric alcohol (with a molecular weight of 4000) (with a mass ratio of 1: 6); the other polyhydric alcohols are a mixture of poly (phthalic acid) glycol ester diol and sorbitol (the mass ratio is 3: 1); the micromolecular diol is a mixture of 1, 4-butanediol, propylene glycol and 1, 4-cyclohexanediol, and the mass ratio of the micromolecular diol to the propylene glycol is 4:1: 2.
A method for preparing PPC resin derivatives, comprising the steps of:
(1) simultaneously heating polyol, toluene diisocyanate, micromolecular diol and bismuth nitrate to 80 ℃, and mixing to obtain a mixture A;
(2) and (3) injecting the mixture A into a feed inlet of a double-screw extruder through a casting machine, reacting for 3 minutes at the temperature of 360mm multiplied by 15 sections, 1-7 sections at 170 ℃ and 8-15 sections at 200 ℃, granulating under water at 60 ℃, and drying to obtain the compound A.
Example 4
The PPC resin derivative comprises the following raw materials in parts by weight: 100 parts of polyol, 35 parts of isophorone diisocyanate, 10 parts of small molecular diol and 0.15 part of tert-butoxytin, wherein the polyol is a mixture of polycarbonate polyol and other polyol (the molar ratio is 14: 1).
The polycarbonate polyol is a mixture of polyethylene carbonate polyol (with a molecular weight of 2500) and polypropylene carbonate polyol (with a molecular weight of 2500) (with a mass ratio of 1: 4); the other polyhydric alcohol is a mixture of poly (phthalic acid) glycol ester diol and sorbitol (the mass ratio is 2.5: 1); the micromolecular diol is a mixture of 1, 4-butanediol, propylene glycol and 1, 4-cyclohexanediol, and the mass ratio of the micromolecular diol to the propylene glycol is 3:1: 1.
A method for preparing PPC resin derivatives, comprising the steps of:
(1) simultaneously heating polyol, isophorone diisocyanate, micromolecular diol and tert-butoxytin to 65 ℃, and mixing to obtain a mixture A;
(2) and (3) injecting the mixture A into a feed inlet of a double-screw extruder through a casting machine, reacting for 2 minutes at the temperature of 360mm multiplied by 15 sections, the temperature of 1-7 sections being 140 ℃ and the temperature of 8-15 sections being 175 ℃, and granulating under water at the temperature of 45 ℃ and drying to obtain the compound A.
Example 5
The only difference from example 4 is that 20 parts of polyethylene glycol was also included.
A method for preparing PPC resin derivatives, comprising the steps of:
(1) simultaneously heating polyol, isophorone diisocyanate, micromolecular diol and tert-butoxytin to 65 ℃, and mixing to obtain a mixture A;
(2) and (3) injecting the mixture A into a feed inlet of a double-screw extruder through a casting machine, wherein the temperature of the mixture A is 360mm multiplied by 15 sections, the temperature of the mixture A is 1-7 sections is 140 ℃, the temperature of the mixture A is 175 ℃ between 8 and 15 sections, after 0.5 minute, polyethylene glycol is added, the mixture is extruded after 2 minutes of reaction, and the mixture is granulated under water at the temperature of 45 ℃ and dried to obtain the polyethylene glycol.
Example 6
The only difference from example 4 is that 40 parts of polyethylene glycol was also included.
A method for preparing PPC resin derivatives, comprising the steps of:
(1) simultaneously heating polyol, isophorone diisocyanate, micromolecular diol and tert-butoxytin to 65 ℃, and mixing to obtain a mixture A;
(2) and (3) injecting the mixture A into a feed inlet of a double-screw extruder through a casting machine, wherein the temperature of the mixture A is 360mm multiplied by 15 sections, the temperature of the mixture A is 1-7 sections is 140 ℃, the temperature of the mixture A is 8-15 sections is 175 ℃, adding polyethylene glycol after 1 minute, reacting for 2 minutes, extruding, granulating under water at 45 ℃, and drying to obtain the polyethylene glycol.
Comparative example 1
The only difference from example 4 is that the molar ratio of polycarbonate polyol to other polyols is 7:1, and the other conditions are the same.
Comparative example 2
The only difference from example 4 is that the other polyol is a mixture of poly (phthalic acid) glycol ester diol and sorbitol in a mass ratio of 4:1, and the rest conditions are the same.
Comparative example 3
The method is different from the method in example 4 only in that the small molecular diol is a mixture of 1, 4-butanediol, propylene glycol and 1, 4-cyclohexanediol, the mass ratio is 1:1:4, and the rest conditions are the same.
Comparative example 4
The only difference from example 4 is that the temperature of the twin-screw extruder at sections 1 to 15 was 175 ℃ during the production of the PPC resin derivative, and the conditions were the same.
Test example 1
The PPC resin derivatives of examples 1-6 and comparative examples 1-4 are tested for mechanical properties, the specific test method refers to GB/T31124-2014, and the sample is type 1A in GB/T1040.2-2006.
The results are shown in Table 1.
TABLE 1PPC resin derivatives mechanical Properties testing
Figure BDA0002246219620000071
Figure BDA0002246219620000081
Test example 2
The in-line modified PPC resins of examples 1,4, 5-6 and comparative examples 1, 3-4 were subjected to biodegradation tests, see GB/T19277-2003. The higher the percentage of biodegradation after 45 days, the better the degree of degradation.
The results are shown in Table 2.
TABLE 2 biodegradation Properties of PPC resin derivatives
After 45d the rate of biodegradation/%)
Example 1 71.8
Example 4 75.1
Example 5 81.4
Example 6 83.9
Comparative example 1 66.5
Comparative example 3 64.3
Comparative example 4 62.0
The technical means disclosed by the scheme of the invention are not limited to the technical means disclosed by the technical means, and the technical scheme also comprises the technical scheme formed by any combination of the technical characteristics. While the foregoing is directed to embodiments of the present invention, it will be appreciated by those skilled in the art that various changes may be made in the embodiments without departing from the principles of the invention, and that such changes and modifications are intended to be included within the scope of the invention.

Claims (7)

1. The PPC resin derivative comprises the following raw materials in parts by weight: 100 parts of polyol, 15-60 parts of isocyanate, 2.4-17 parts of small molecular diol and 0.1-0.2 part of catalyst, wherein the polyol is a mixture of polycarbonate polyol and other polyols, and the molar ratio of the polycarbonate polyol to the other polyols is 12-15: 1;
the other polyalcohol is a mixture of other polyester polyalcohol and sorbitol; the PPC resin derivative also comprises 20-40 parts of polyethylene glycol;
the mass ratio of the other polyester polyols to the sorbitol is 2-3: 1;
the micromolecular diol is a mixture of 1, 4-butanediol, propylene glycol and 1, 4-cyclohexanediol; the mass ratio of the 1, 4-butanediol, the propylene glycol and the 1, 4-cyclohexanediol is 2-4:1: 0.5-2;
the preparation method of the PPC resin derivative comprises the following steps:
(1) mixing polyalcohol, isocyanate, micromolecular diol and a catalyst to obtain a mixture A;
(2) and injecting the mixture A into a feed inlet of a double-screw extruder through a casting machine, wherein the temperature of 360mm multiplied by 15 sections is 130-.
2. The PPC resin derivative according to claim 1, wherein said polycarbonate polyol is a polypropylene carbonate polyol or a mixture of a polyethylene carbonate polyol and a polypropylene carbonate polyol, said polypropylene carbonate polyol having a molecular weight of 1500-4000 and a functionality of 2.
3. The PPC resin derivative according to claim 1, wherein said other polyester polyol is at least one of polyethylene glycol adipate glycol, 1, 4-butylene glycol adipate glycol, diol sebacate glycol, and diol polyphthalate glycol.
4. The PPC resin derivative according to claim 1, wherein said isocyanate is at least one of 4,4 '-diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, 4' -dicyclohexylmethane diisocyanate and hexamethylene diisocyanate.
5. The PPC resin derivative according to claim 1, wherein said catalyst comprises at least one of tin, bismuth and butyl titanate.
6. A process for the preparation of the PPC resin derivative according to any of claims 1-5, comprising the steps of:
(1) mixing polyalcohol, isocyanate, micromolecular diol and a catalyst to obtain a mixture A;
(2) and injecting the mixture A into a feed inlet of a double-screw extruder through a casting machine, wherein the temperature of 360mm multiplied by 15 sections is 130-.
7. The production method according to claim 6, wherein the step (1) comprises the steps of: heating the polyalcohol, the isocyanate, the micromolecular diol and the catalyst to 50-80 ℃ at the same time, and mixing to obtain a mixture A.
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