Environment-friendly macromolecular modified PVC (polyvinyl chloride) composition

Abstract

The invention discloses an environment-friendly macromolecular modifier PVC (polyvinyl chloride) composition, and belongs to the technical field of polyvinyl chloride materials. The composition comprises the following components in parts by weight: 100 parts of PVC, 1-50 parts of a polycarbonate toughening modifier and 0-30 parts of an auxiliary agent. The polycarbonate toughening modifier with a certain polymerization degree is used as the modifier of the PVC material, the plasticity, toughness, impact resistance and other properties of PVC can be obviously improved, the polycarbonate toughening modifier is a macromolecular polymer and cannot be separated out in the use process, the safety of the PVC material is improved, and the service life of the PVC material is prolonged.

Description

Technical Field

[0001] The invention belongs to the technical field of polyvinyl chloride materials, and in particular relates to an environmentally friendly macromolecular modifier PVC composition. Background Art

[0002] Polyvinyl chloride (PVC) is widely used in many fields due to its good physical properties and chemical stability. However, PVC itself has some shortcomings, such as high brittleness, poor thermal stability, poor processing fluidity, etc., which limit its application. In order to improve these properties, plasticizers, toughening agents, thermal stabilizers and other additives are usually added to PVC resin. Traditional plasticizers, such as phthalates (DOP, etc.), can effectively increase the plasticity and flexibility of PVC, but there is a problem of easy precipitation. Because the precipitated plasticizers are harmful to the human body and the environment, such plasticizers have been banned in many countries.

[0003] In addition, during long-term use, the precipitation of such plasticizers will also cause the performance of PVC materials to deteriorate.

[0004] For example, patent CN103897298B discloses a corrosion-resistant, wear-resistant and aging-resistant modified PVC plastic composition. This patent enables PVC polyvinyl chloride to have excellent properties such as corrosion resistance, wear resistance, ability to withstand higher pressure, not easy to form dead folds and resistance to a certain negative pressure. However, the plasticizer used therein also belongs to the phthalate plasticizer, and there is the problem of precipitation of the above-mentioned additives.

[0005] Patent CN103788406A discloses a bio-based environmentally friendly plasticizer that can completely replace DOP. The plasticizer is composed of the following weight percentages: 15-50% epoxy vegetable oil; 1-50% epoxy fatty acid methyl ester; 0-50% epoxy fatty acid polyol ester; and the balance of cold-resistant plasticizer. Although this formula can solve the problem of harm to the human body after the plasticizer precipitates, the material performance still decreases after precipitation, affecting the service life. Summary of the invention

[0006] The technical problem to be solved by the present invention is to overcome the deficiencies of the prior art and provide an environmentally friendly macromolecular modifier PVC composition which does not contain harmful plasticizers and has a longer service life.

[0007] The technical solution adopted by the present invention to solve the technical problem is: an environmentally friendly macromolecular modifier PVC composition, characterized in that the composition by weight includes: 100 parts of PVC, 1-50 parts of polycarbonate toughening modifier, and 0-30 parts of auxiliary agent. The polycarbonate toughening modifier is a block structure including a rigid segment and a flexible segment. The rigid segment A is a PE segment polymerized by epoxy compound and cyclic acid anhydride or / and a polycarbonate segment of epoxy cyclohexane and CO2; the flexible segment B is one or more of a polycarbonate segment of a long-chain epoxy compound and carbon dioxide, a self-polymerized segment of a long-chain epoxy compound, or PPO, and the long-chain epoxy compound is a C4-C20 epoxy compound.

[0008] The present invention adopts a polycarbonate toughening modifier as a modifier of the PVC material, which can significantly improve the plasticity, toughness and impact resistance of the PVC. The polycarbonate toughening modifier itself is a macromolecular polymer and will not precipitate during use, thereby improving the safety and life of the PVC material.

[0009] Preferably, the polycarbonate toughening modifier is a linear block structure. The polycarbonate toughening modifier with a linear block structure has good flexibility and is used to modify PVC materials to have better plasticizing effect.

[0010] The rigid segment A and the flexible segment B in the polycarbonate toughening modifier with a linear block structure can be arranged in a variety of ways, such as AB type, ABA type, BAB type, ABAB type, etc. More preferably, the linear block structure is a molecular chain in which the rigid segment A and the flexible segment B are connected to form an ABA-type block structure. In this structure, the two ends are rigid and the middle is flexible. After the PVC material is modified, the material has higher strength and better flexibility.

[0011] Optionally, the polycarbonate toughening modifier comprises a polycarbonate having the following structure: n —C, wherein A is a polycarbonate chain, n is 2 to 4, and C is a multi-head initiator residue; the polycarbonate chain is a block structure of a flexible segment and a rigid segment.

[0012] This type of polycarbonate toughening modifier has a star-shaped structure. After mixing with PVC, the molecular entanglement is more complicated and more difficult to precipitate. However, the toughening and plasticizing effect is slightly worse than that of the linear block structure.

[0013] Specifically, the polycarbonate toughening modifier is used as a polycarbonate type impact resistant agent, and the polycarbonate type impact resistant agent has the following structure: A n —C, wherein A is a polycarbonate chain, n is 2 to 4, and C is a multi-head initiator residue; the polycarbonate chain is a block structure of a flexible segment and a rigid segment, one end of the flexible segment is connected to the multi-head initiator residue, and the other end of the flexible segment is connected to the rigid segment.

[0014] The polycarbonate toughening modifier is an impact-resistant agent for polymer elastomers, has a star-shaped structure, and the flexible segments are centrally connected to the multi-head initiator residues, with rigid segments on the outside. It will not precipitate after being mixed with PVC, and the processing temperature is compatible with PVC. After being blended with PVC, it can meet the requirements of toughening and impact resistance.

[0015] Preferably, the number average molecular weight of the polycarbonate chain in the impact modifier is 2500-15W. The preferred molecular weight can meet the toughening and impact resistance requirements of most PVC. More preferably, the number average molecular weight of the polycarbonate chain is 5W-12W, which is suitable for PVC applications with higher impact performance requirements.

[0016] More preferably, the structural formula of the polycarbonate chain described in the impact modifier used is:

[0017] ,

[0018] Wherein, a, b, c, d are all integers, and 1≤a+b≤90, 1≤c+d+e≤85; R1 is hydrogen or methyl, R2 is butyl, C12 alkyl or C14 alkyl, and R3 is C1~C14 alkyl.

[0019] Preferably, the ratio of a+b to c+d+e is 1:1.2-1.5. When the ratio of the outer rigid segment is adjusted to be slightly higher than that of the inner flexible segment, the impact resistance can be better exhibited as an impact resistance agent in PVC.

[0020] Specifically, the general formula of C in the impact modifier used is R(-L)n, and R(-L)n is an n-valent anionic group derived from (A) a nitrogen-free aliphatic organic polycarboxylic acid, (B) a polyphenol, (C) polyacrylic acid, acrylic acid-methacrylic acid copolymer or polymaleic acid, (D) a hydroxyaromatic carboxylic acid, or (E) a nitrogen-containing aliphatic organic polycarboxylic acid.

[0021] Preferably, the C is:

[0022] ,

[0023] ,

[0024] ,

[0025] ,

[0026] ,

[0027] ,

[0028] and

[0029] The above preferred initiator residue has good flexibility and is suitable as the copolymer core of the impact resistance agent.

[0030] A preparation process A of the above-mentioned polycarbonate type impact resistant agent is as follows:

[0031] 1) placing an epoxy compound, a catalyst and a multi-head initiator into a high-pressure reactor, wherein the epoxy compound is propylene oxide and / or ethylene oxide, and performing a polymerization reaction at a reaction temperature of 55° C. to 75° C. for 5 to 15 hours;

[0032] 2) After the reaction is completed, the temperature is lowered to 40°C~50°C, cyclohexene oxide is added, and carbon dioxide is introduced until the pressure reaches 2.5MPa~4.0MPa, and the polymerization reaction is carried out for 5~10 hours, and then post-treatment is performed to obtain the product.

[0033] Another preparation process B of the above-mentioned polycarbonate type impact resistant agent is as follows:

[0034] 1) Putting an epoxy compound, a catalyst and a multi-head initiator into a high-pressure reactor, wherein the epoxy compound is BGE and / or AGE, introducing carbon dioxide until the pressure reaches 2.5MPa~4.0MPa, and performing polymerization reaction at 40℃~50℃ for 5~10 hours;

[0035] 2) After the reaction is completed, the gas in the kettle is replaced with nitrogen, and then an epoxy compound and phthalic anhydride are added into the kettle. The epoxy compound is propylene oxide and / or ethylene oxide, and the reaction temperature is increased to 55°C to 75°C for polymerization reaction for 5 to 15 hours.

[0036] The present invention provides two copolymerization processes, which can prepare polycarbonate-type impact resistant agents satisfying the above structure with high yield, and other molecular structures need to be adjusted in a targeted manner.

[0037] In the above-mentioned preparation processes A and B, the catalyst can be a metal catalyst or an organic boron compound, and the metal catalyst includes a zinc catalyst system, a metal porphyrin catalyst system, a β-diimine metal complex catalyst, a double metal cyanide complex catalyst, a SalenMX catalyst system, a rare earth catalyst system, and a multi-metal catalyst system.

[0038] In preparation process A, the catalyst is triethyl boron, tripropyl boron or tributyl boron. In preparation process A, only short alkyl organic boron needs to be selected to cooperate with multi-head initiator to achieve high yield copolymerization and obtain the target product with good performance as an impact resistance agent.

[0039] In preparation process B, the catalyst is a composite catalyst of triethyl boron and diphenylboric acid in a molar ratio of 2.3 to 3.6:1. In preparation process B, long-chain BGE and / or AGE need to be copolymerized with CO2 to obtain polycarbonate segments, and phthalic anhydride and epoxy compounds need to be catalyzed for copolymerization. A specific catalyst ratio is required to ensure the acquisition of the target product. Under the preferred catalyst ratio, copolymers with the desired structure can be obtained by copolymerization with high yield, and as an impact resistance agent, the copolymers have excellent performance.

[0040] Specifically, the polycarbonate toughening modifier is used as a polycarbonate plasticizer, and the polycarbonate plasticizer has the following structure: B m —S, wherein B is a polycarbonate chain, m is 2 to 4, and S is a multi-head initiator residue; the polycarbonate chain is a block structure of a rigid segment and a flexible segment, one end of the rigid segment is connected to the multi-head initiator residue, and the other end of the rigid segment is connected to the flexible segment.

[0041] The novel polycarbonate plasticizer for PVC used in the present invention has a star-shaped structure, wherein the rigid segments are centrally connected to the multi-head initiator residues, and the outer side is a flexible segment. The plasticizer has not only excellent plasticizing effect and long-term stability, but also low migration and good environmental adaptability. Through innovative molecular design, the plasticizer can significantly reduce the potential risks to human body and environment while maintaining the flexibility and processing performance of PVC materials, thus meeting the demand of modern industry for high-performance and environmentally friendly plasticizers.

[0042] Preferably, the number average molecular weight of the polycarbonate chain in the plasticizer is 2000-12W. The preferred molecular weight can meet the plasticization requirements of most PVC. More preferably, the number average molecular weight of the polycarbonate chain is 4W-8W, which is suitable for PVC applications with higher requirements for ductility.

[0043] Preferably, the structural formula of the polycarbonate chain described in the plasticizer used is:

[0044] ,

[0045] Wherein, f, g, h, i, j are all integers, and 1≤f+g+h≤80, 1≤i+j≤95; R4 is a C1~C14 alkyl group, R5 is hydrogen or methyl, and R6 is a butyl group, a C12 alkyl group or a C14 alkyl group.

[0046] More preferably, the ratio of f+g+h to i+j is 1:1.2-1.5. When the ratio of the outer flexible segment is adjusted to be slightly higher than that of the inner rigid segment, the plasticizer exhibits better flexibility.

[0047] Specifically, the general formula of S in the plasticizer used is R(-L) m, R(-L) m It is an m-valent anionic group derived from (A) a nitrogen-free aliphatic organic polycarboxylic acid, (B) a polyphenol, (C) polyacrylic acid, acrylic acid-methacrylic acid copolymer or polymaleic acid, (D) a hydroxyaromatic carboxylic acid, or (E) a nitrogen-containing aliphatic organic polycarboxylic acid.

[0048] Preferably, the S is:

[0049] ,

[0050] ,

[0051] and

[0052] One, two or more of the following.

[0053] Preferably, the preparation process 1 of the polycarbonate plasticizer is:

[0054] 1) Add cyclohexene oxide, catalyst and multi-head initiator into the reactor, introduce carbon dioxide until the pressure reaches 2.5MPa~4.0MPa, control the reaction temperature at 40℃~50℃, and carry out polymerization reaction for 5~10 hours;

[0055] 2) After nitrogen substitution in the reactor, an epoxy compound is added, wherein the epoxy compound is propylene oxide and / or ethylene oxide, and the temperature is raised to a reaction temperature of 55° C. to 75° C. and then the polymerization reaction is continued for 5 to 15 hours; and then post-treatment is performed to obtain the product.

[0056] Preferably, the preparation process 2 of the polycarbonate plasticizer is:

[0057] 1) Adding an epoxy compound 1, a phthalic anhydride catalyst and a multi-head initiator into a reaction kettle, wherein the epoxy compound 1 is propylene oxide and / or ethylene oxide, raising the reaction temperature to 55° C. to 75° C. and performing a polymerization reaction for 5 to 10 hours;

[0058] 2) Putting the epoxy compound 2 into a reaction kettle, wherein the epoxy compound 2 is BGE and / or AGE, introducing carbon dioxide until the pressure reaches 2.5MPa~4.0MPa, and performing polymerization reaction at 40℃~50℃ for 8~15 hours; then performing post-treatment to obtain the product.

[0059] The present invention provides two copolymerization processes, which can prepare polycarbonate plasticizers satisfying the above structure with high yield, and other molecular structures need to be adjusted in a targeted manner.

[0060] Preferably, in the preparation processes A and B of the above-mentioned polycarbonate plasticizer, the catalyst is a metal catalyst or an organic boron compound, and the metal catalyst includes a zinc catalyst system, a metal porphyrin catalyst system, a β-diimine metal complex catalyst, a double metal cyanide complex catalyst, a SalenMX catalyst system, a rare earth catalyst system, and a multi-metal catalyst system.

[0061] Preferably, in the preparation process 1 of the polycarbonate plasticizer, the catalyst is triethyl boron, tripropyl boron or tributyl boron. In the preparation process 1, only short alkyl organic boron needs to be selected to cooperate with the multi-head initiator to achieve high-yield copolymerization and obtain the target product with good plasticizing properties.

[0062] Preferably, in the preparation process 2 of the polycarbonate plasticizer, the catalyst is triethyl boron and diphenylboric acid in a molar ratio of 2.3 to 3.6:1. In the preparation process 2, long-chain BGE and / or AGE need to be copolymerized with CO2 to obtain polycarbonate segments, and phthalic anhydride and epoxy compounds need to be catalyzed for copolymerization. A specific catalyst is required for the ratio to ensure the acquisition of the target product. Under the preferred catalyst ratio, a copolymer with a desired structure can be obtained by copolymerization with a high yield, and as a plasticizer, the performance is excellent.

[0063] In the above-mentioned preparation process of the impact modifier and plasticizer, R(-L)n and R(-L) m All can be selected from (A) nitrogen-free aliphatic or aromatic organic polycarboxylic acid, (B) polyphenol, (C) polyacrylic acid, acrylic acid-methacrylic acid copolymer or polymaleic acid, (D) hydroxy aromatic carboxylic acid, or (E) n-valent anionic groups derived from nitrogen-containing aliphatic or aromatic organic polycarboxylic acid; -L is -COO- (carboxylate) or -O- (oxygen); MR'x is a cationic group ammonium ion (quaternary ammonium cation), sulfonium ion (quaternary uranium cation) or phosphonium ion (quaternary phosphonium cation) and H is a hydrogen ion (H+). R' is a C1~C30 hydrocarbon group, preferably a C2~C20 hydrocarbon group, more preferably a C2~C10 hydrocarbon group, more preferably a C2~C5 hydrocarbon group, such as ethyl, propyl or butyl.

[0064] x is 3 or 4. When MR'x is an ammonium ion (quaternary ammonium cation) or a phosphonium ion (quaternary phosphonium cation), x is 4, and when MR'x is a sulfonium ion (quaternary sarsenium cation), x is 3. M is N (nitrogen), P (phosphorus) or S (sulfur).

[0065] m, n are the total number of carboxylic acids and / or phenolic hydroxyl groups in the polycarboxylic acids or polyphenols of (A) to (E). M, n are generally integers of 2 to 30, preferably 3 to 29, more preferably 4 to 28, for example 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27.

[0066] Preferably, the nitrogen-free aliphatic or aromatic polycarboxylic acid (A) is (or is selected from): (A1) (hydroxyl-free or hydroxyl-containing) C6-C30 (preferably C8-C20, more preferably C10-C16) aliphatic or aromatic organic polycarboxylic acid (such as 1,4-butanedicarboxylic acid, pentane-1,3,5-tricarboxylic acid, citric acid, malic acid, o-, m-, p-terephthalic acid, benzene trimecartonic acid, pyromellitic acid, naphthalene dicarboxylic acid, naphthalene trimecartonic acid, naphthalene tetracarboxylic acid, naphthalene pentacarboxylic acid, naphthalene hexacarboxylic acid).

[0067] Preferably, the polyphenol (B) is (or is selected from) C6-C30 (preferably C6-C20) polyphenol. More preferably, the polyphenol (C) is (or is selected from): o-, m- and p-quinone, naphthalene-tetraphenol, bisphenol A, bisphenol F, bisphenol S.

[0068] Preferably, the polyacrylic acid, acrylic acid-methacrylic acid copolymer or polymaleic acid (C) is a polyacrylic acid, acrylic acid-methacrylic acid copolymer or polymaleic acid having a number average molecular weight of 220-2000 (preferably 290-1500, more preferably 350-1000 or 500-900, such as 216, 258, 348, 600, 700 or 800).

[0069] Preferably, the hydroxyaromatic carboxylic acid (D) is a hydroxyaromatic polycarboxylic acid or a polyhydroxyaromatic carboxylic acid. Preferably, the hydroxyaromatic carboxylic acid (D) is (or is selected from): hydroxyphthalic acid, ...

[0070] Preferably, the nitrogen-containing aliphatic or aromatic organic polycarboxylic acid (E) is (or is selected from): (E1) C2-C30 (preferably C3-C28, more preferably C4-C24) alkylenediaminetetra(C2-C6)carboxylic acid, or nitrilotri(C2-C6)carboxylic acid; for example, ethylenediaminetetraacetic acid, ethylenediaminetetrapropionic acid, ethylenediaminetetrabutyric acid, ethylenediaminetetrapentanoic acid, ethylenediaminetetrahexanoic acid, propylenediaminetetraacetic acid, propylenediaminetetrapropionic acid, propylenediaminetetrabutyric acid, propylenediaminetetrapentanoic acid, propylenediaminetetrahexanoic acid, butylene diamine tetraacetic acid, butanediaminetetrapropionic acid, butanediaminetetrabutyric acid, butanediaminetetrapentanoic acid, butanediaminetetrahexanoic acid, nitrilotriacetic acid, nitrilotripropionic acid, nitrilotributyric acid, nitrilotripovaleric acid, or nitrilotrihexanoic acid; or, (E2) N-C1-C4 alkyl-piperidinedicarboxylic acid (such as N-methyl-piperidine-3,5-dicarboxylic acid), N-C1-C4 alkyl-piperidinetricarboxylic acid (such as N-ethyl-piperidinetricarboxylic acid), or N-C1-C4 alkyl-piperidinetetracarboxylic acid (such as N-ethyl-piperidinetetracarboxylic acid).

[0071] Preferably, R is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a nitrogen-containing aliphatic hydrocarbon group, or a nitrogen-containing aromatic hydrocarbon group.

[0072] According to a second embodiment of the present invention, there is provided a fully onium salted (i.e., fully salified, fully neutralized, and free of H+) multifunctional onium salt initiator (or multi-arm macromolecular initiator) having the following general formula (II):

[0073]

R(-L)n

(MR′x)n

[0074] Here, MR'x is a cationic group such as a sulfonium ion (quaternary sulfonium cation) or a phosphonium ion (quaternary phosphonium cation).

[0075] wherein R(-L)n, R, -L, M, R', n and x are as defined above.

[0076] The inventors of the present application have found that, despite being completely onium salted, the initiator of the general formula II containing a sulfonium ion (quaternary stibnium cation) or a phosphonium ion (quaternary phosphonium cation) still has a high reactivity.

[0077] According to a third embodiment of the present invention, there is provided a fully onium salted (i.e., fully salified, fully neutralized, and free of H+) multifunctional onium salt initiator (or multi-arm macromolecular initiator) having the following general formula (III):

[0078]

R(-L)n

(MR′x)n

[0079] In the formula, R(-L)n is an n-valent anionic group derived from the above-mentioned (E) nitrogen-containing aliphatic or aromatic organic polycarboxylic acid;

[0080] wherein R, -L, M, R', n and x are as defined above.

[0081] Here, MR'x is a cationic group such as ammonium ion (quaternary ammonium cation), sulfonium ion (quaternary stibnium cation) or phosphonium ion (quaternary phosphonium cation).

[0082] The additives can be added according to the needs of different usage scenarios, including heat stabilizers, lubricants, fillers, anti-aging agents and colorants, etc. The heat stabilizer is used to prevent the thermal decomposition of PVC during processing. Common heat stabilizers include lead salts, metal soaps, organic tin, etc. Lubricants improve the processing properties of PVC, reduce friction, and improve fluidity. Common lubricants include metal soaps such as stearic acid, calcium stearate, lead stearate, and fatty acid esters such as butyl stearate and glycerol monostearate. Fillers are used to improve the physical properties of PVC and reduce costs. Common fillers include calcium carbonate, talcum powder, etc. Anti-aging agents extend the service life of PVC products and prevent aging caused by light, oxygen, heat, etc. Common anti-aging agents include ultraviolet absorbers, light stabilizers, etc. Colorants give PVC products a specific color.

[0083] Preferably, the auxiliary agent includes 0-20 parts by weight of a processing lubricant and 0-10 parts by weight of a heat stabilizer.

[0084] Further preferably, the processing lubricant is polypropylene carbonate (PC), and the preferred addition amount is 5 to 20 parts. The present invention uses PC as a processing lubricant, which not only has a good lubricating effect, but also has a plasticizing effect. More importantly, the addition of PC can also increase the compatibility of PVC and polycarbonate toughening modifiers. It is particularly suitable for application in soft PVC materials.

[0085] Compared with the prior art, the present invention has the following beneficial effects: the present invention significantly improves the plasticity, toughness and impact resistance of PVC by using a polycarbonate toughening modifier. As a macromolecular polymer, this modifier will not precipitate during the use of PVC, thereby improving the safety and life of the material. The polycarbonate toughening modifier of the present invention has a star-shaped structure, so that the modifier will not precipitate after mixing with PVC, and the processing temperature matches that of PVC, meeting the requirements of toughening and impact resistance, and having low migration and good environmental adaptability. This not only maintains the flexibility and processing performance of the PVC material, but also significantly reduces the potential risks to the human body and the environment, and meets the needs of modern industry for high-performance, environmentally friendly plasticizers. In addition, the polymer structure of the polycarbonate toughening modifier provides excellent plasticizing effect and long-term stability. Compared with traditional plasticizers, the polycarbonate plasticizer has better durability and prolongs the service life of the product. The low migration of the polycarbonate toughening modifier also reduces the risk of the plasticizer migrating from the PVC product to the human body or the environment, reducing the potential threat to human health. The invention also improves the processing performance of PVC, so that the PVC products have better flexibility and processability. DETAILED DESCRIPTION

[0086] The present invention is described in detail below by way of examples. Unless otherwise specified, all raw materials used are commercially available.

[0087] Preparation of polycarbonate type impact resistant agent A

[0088] 1) Propylene oxide, triethyl boron and The mixture was put into a high pressure reactor at a molar ratio of 100:0.01:0.08, and the polymerization reaction was carried out at a reaction temperature of 65°C for 10 hours;

[0089] 2) After the reaction is completed, the temperature is lowered to 45°C, cyclohexene oxide is added, and carbon dioxide is introduced until the pressure reaches 3.5MPa. The molar ratio of cyclohexene oxide to propylene oxide in step 1) is 135:100. The polymerization reaction is carried out for 7 hours. After the reaction is complete, the reaction is terminated to obtain a glue solution; the glue solution is washed and devolatilized. The number average molecular weight of the obtained copolymer is 30W according to nuclear magnetic resonance detection, of which the molar percentage of the PPO flexible segment is 42.6%, and the molar percentage of the polycarbonate rigid segment of cyclohexene oxide and CO2 is 57.4%.

[0090] Preparation of polycarbonate type impact resistant agent B

[0091] 1) Ethylene oxide, tripropyl boron and The mixture was put into a high pressure reactor in a molar ratio of 100:0.01:0.069, and the polymerization reaction was carried out at a reaction temperature of 55° C. for 15 hours;

[0092] 2) After the reaction is completed, the temperature is lowered to 40°C, cyclohexene oxide is added and carbon dioxide is introduced until the pressure reaches 4.0MPa, the molar ratio of cyclohexene oxide to ethylene oxide in step 1) is 150:100, and the polymerization reaction is carried out for 10 hours. After the reaction is complete, the reaction is terminated to obtain a glue solution; the glue solution is washed and devolatilized to obtain the obtained copolymer. The number average molecular weight of the obtained copolymer detected by nuclear magnetic resonance is 36W, of which the molar percentage of the PEO flexible segment is 40%, and the molar percentage of the polycarbonate rigid segment of cyclohexene oxide and CO2 is 60%.

[0093] Preparation of polycarbonate type impact resistant agent C

[0094] 1) Propylene oxide, tributyl boron and Putting the epoxy compound into a high pressure reactor in a molar ratio of 100:0.01:0.11, wherein the epoxy compound is propylene oxide and / or ethylene oxide, and carrying out polymerization reaction at a reaction temperature of 75° C. for 5 hours;

[0095] 2) After the reaction is completed, the temperature is lowered to 50°C, cyclohexene oxide is added, and carbon dioxide is introduced until the pressure reaches 2.5MPa. The molar ratio of cyclohexene oxide to propylene oxide is 120:100. The polymerization reaction is carried out for 5 hours. After the reaction is complete, the reaction is terminated to obtain a glue solution; the glue solution is washed and devolatilized. The number average molecular weight of the obtained copolymer is 20W according to nuclear magnetic resonance detection, of which the molar percentage of the PPO flexible segment is 45.5%, and the molar percentage of the polycarbonate rigid segment of cyclohexene oxide and CO2 is 54.5%.

[0096] Preparation of polycarbonate type impact resistant agent D

[0097] 1) Propylene oxide, triethyl boron and The mixture was put into a high pressure reactor in a molar ratio of 100:0.01:0.13, and the polymerization reaction was carried out at a reaction temperature of 65° C. for 10 hours;

[0098] 2) After the reaction is completed, the temperature is lowered to 45°C, cyclohexene oxide is added, and carbon dioxide is introduced until the pressure reaches 3.5MPa. The molar ratio of cyclohexene oxide to propylene oxide in step 1) is 233:100. The polymerization reaction is carried out for 7 hours. After the reaction is complete, the reaction is terminated to obtain a glue solution; the glue solution is washed and devolatilized. The number average molecular weight of the obtained copolymer is 30W according to nuclear magnetic resonance detection, of which the molar percentage of the PPO flexible segment is 30%, and the molar percentage of the polycarbonate rigid segment of cyclohexene oxide and CO2 is 70%.

[0099] Preparation of polycarbonate type impact resistant agent E

[0100] 1) AGE, catalyst and Put the catalyst in a high pressure reactor in a molar ratio of 100:0.01:0.164, which is a composite catalyst of triethyl boron and diphenylboric acid in a molar ratio of 3.0:1; introduce carbon dioxide until the pressure reaches 3.5 MPa, and carry out polymerization reaction at 45°C for 8 hours;

[0101] 2) After the reaction is completed, the gas in the kettle is replaced with nitrogen, and then propylene oxide and phthalic anhydride are added to the kettle. The molar ratio of AGE to propylene oxide and phthalic anhydride in step 1) is 100:130:130, and the reaction temperature is increased to 65°C for polymerization reaction for 10 hours. After the reaction is complete, the reaction is terminated to obtain a glue solution; the glue solution is washed and devolatilized. The number average molecular weight of the obtained copolymer is 30W according to nuclear magnetic resonance detection, of which the molar percentage of the polycarbonate flexible segment of AGE and CO2 is 43.4%, and the molar percentage of the PE rigid segment polymerized by propylene oxide and phthalic anhydride is 56.6%.

[0102] Preparation of polycarbonate type impact resistant agent F

[0103] 1) AGE, catalyst and Put the catalyst into a high-pressure reactor in a molar ratio of 100:0.01:4.5, triethyl boron and diphenylboric acid in a molar ratio of 2.3:1; introduce carbon dioxide until the pressure reaches 2.5MPa, and carry out polymerization reaction at 50°C for 10 hours;

[0104] 2) After the reaction is completed, the gas in the kettle is replaced with nitrogen, and then ethylene oxide and phthalic anhydride are added to the kettle. The molar ratio of AGE to ethylene oxide and phthalic anhydride in step 1) is 100:120:120, and the reaction temperature is increased to 55°C for polymerization for 15 hours. After the reaction is complete, the reaction is terminated to obtain a glue solution; the glue solution is washed and devolatilized. The number average molecular weight of the obtained copolymer is 1W according to nuclear magnetic resonance detection, of which the molar percentage of the polycarbonate flexible segment of AGE and CO2 is 45.5%, and the molar percentage of the PE rigid segment polymerized by ethylene oxide and phthalic anhydride is 54.5%.

[0105] Preparation of polycarbonate type impact resistant agent G

[0106] 1) Combine BGE, catalyst and Put the catalyst into a high-pressure reactor in a molar ratio of 100:0.01:0.12, triethyl boron and diphenylboric acid in a molar ratio of 3.6:1; introduce carbon dioxide until the pressure reaches 4.0 MPa, and carry out polymerization reaction at 40°C for 5 hours;

[0107] 2) After the reaction is completed, the gas in the kettle is replaced with nitrogen, and then propylene oxide and phthalic anhydride are added to the kettle. Step 1) The molar ratio of BGE to propylene oxide and phthalic anhydride is 100:150:150, and the reaction temperature is increased to 75°C for polymerization reaction for 5 hours. After the reaction is complete, the reaction is terminated to obtain a glue solution; the glue solution is washed and devolatilized. The number average molecular weight of the obtained copolymer is 45W according to nuclear magnetic resonance detection, of which the molar percentage of the polycarbonate flexible segment of BGE and CO2 is 40%, and the molar percentage of the PE rigid segment polymerized by propylene oxide and phthalic anhydride is 60%.

[0108] Preparation of polycarbonate type impact resistant agent H

[0109] 1) AGE, catalyst and Put the catalyst in a high pressure reactor in a molar ratio of 100:0.01:0.164, which is a composite catalyst of triethyl boron and diphenylboric acid in a molar ratio of 1:2; introduce carbon dioxide until the pressure reaches 3.5 MPa, and carry out polymerization reaction at 45°C for 8 hours;

[0110] 2) After the reaction is completed, the gas in the kettle is replaced with nitrogen, and then propylene oxide and phthalic anhydride are added to the kettle. The molar ratio of AGE to propylene oxide and phthalic anhydride in step 1) is 100:130:130, and the reaction temperature is increased to 65°C for polymerization reaction for 10 hours. After the reaction is complete, the reaction is terminated to obtain a glue solution; the glue solution is washed and devolatilized. The number average molecular weight of the obtained copolymer is 27W according to nuclear magnetic resonance detection, of which the molar percentage of the polycarbonate flexible segment of AGE and CO2 is 41.8%, and the molar percentage of the PE rigid segment polymerized by propylene oxide and phthalic anhydride is 58.2%.

[0111] Preparation of polycarbonate plasticizer A

[0112] 1) Cyclohexene oxide, triethyl boron and multi-head initiator are placed in a high pressure reactor at a molar ratio of 100:0.01:0.09, wherein the multi-head initiator is ; and introduce carbon dioxide until the pressure reaches 3.5MPa, the reaction temperature is controlled at 45°C, and the polymerization reaction is carried out for 7 hours;

[0113] 2) After nitrogen replacement in the reactor, propylene oxide is added, and the molar ratio of propylene oxide to cyclohexene oxide in step 1) is 135:100. After the temperature is raised to 65°C, the polymerization reaction is continued for 10 hours. After the reaction is complete, the reaction is terminated to obtain a glue solution; the glue solution is washed and devolatilized to obtain a copolymer. The number average molecular weight of the obtained copolymer is 24W according to nuclear magnetic resonance detection, wherein the molar percentage of the polycarbonate rigid segment of cyclohexene oxide and CO2 is 42.3%, and the molar percentage of the PPO flexible segment is 57.7%.

[0114] Preparation of polycarbonate plasticizer B

[0115] 1) Cyclohexene oxide, tripropyl boron and multi-head initiator are placed in a high pressure reactor at a molar ratio of 100:0.01:0.08, wherein the multi-head initiator is ; and introduce carbon dioxide until the pressure reaches 2.5MPa, the reaction temperature is controlled at 50°C, and the polymerization reaction is carried out for 8 hours;

[0116] 2) After nitrogen replacement in the reactor, ethylene oxide is added, and the molar ratio of ethylene oxide to cyclohexene oxide in step 1) is 120:100. After the temperature is raised to 75°C, the polymerization reaction is continued for 9 hours. After the reaction is complete, the reaction is terminated to obtain a glue solution; the glue solution is washed and devolatilized to obtain a copolymer. The number average molecular weight of the obtained copolymer is 24W according to nuclear magnetic resonance detection, wherein the molar percentage of the polycarbonate rigid segment of cyclohexene oxide and CO2 is 45.3%, and the molar percentage of the PEO flexible segment is 54.7%.

[0117] Preparation of polycarbonate plasticizer C

[0118] 1) Cyclohexene oxide, triethyl boron and multi-head initiator are placed in a high pressure reactor at a molar ratio of 100:0.01:0.14, wherein the multi-head initiator is , and introduce carbon dioxide until the pressure reaches 4.0MPa, the reaction temperature is controlled at 40°C, and the polymerization reaction is carried out for 7 hours;

[0119] 2) After nitrogen replacement in the reactor, propylene oxide is added, and the molar ratio of propylene oxide to cyclohexene oxide in step 1) is 150:100. After the temperature is raised to 55°C, the polymerization reaction is continued for 12 hours. After the reaction is complete, the reaction is terminated to obtain a glue solution; the glue solution is washed and devolatilized to obtain a copolymer. The number average molecular weight of the obtained copolymer is 16W according to nuclear magnetic resonance detection, wherein the molar percentage of the polycarbonate rigid segment of cyclohexene oxide and CO2 is 39.2%, and the molar percentage of the PPO flexible segment is 60.8%.

[0120] Preparation of polycarbonate plasticizer D

[0121] 1) Cyclohexene oxide, triethyl boron and multi-head initiator are placed in a high pressure reactor at a molar ratio of 100:0.01:0.13, wherein the multi-head initiator is ; and introduce carbon dioxide until the pressure reaches 3.5MPa, the reaction temperature is controlled at 45°C, and the polymerization reaction is carried out for 5 hours;

[0122] 2) After nitrogen replacement in the reactor, propylene oxide is added, and the molar ratio of propylene oxide to cyclohexene oxide in step 1) is 300:100. After the temperature is raised to 65°C, the polymerization reaction is continued for 16 hours. After the reaction is complete, the reaction is terminated to obtain a glue solution; the glue solution is washed and devolatilized to obtain a copolymer. The number average molecular weight of the obtained copolymer is 24W according to nuclear magnetic resonance detection, wherein the molar percentage of the polycarbonate rigid segment of cyclohexene oxide and CO2 is 42.3%, and the molar percentage of the PPO flexible segment is 57.7%.

[0123] Preparation of polycarbonate plasticizer E

[0124] 1) Propylene oxide, phthalic anhydride, catalyst and multi-head initiator are placed in a high pressure reactor in a molar ratio of 100:100:0.01:0.138, wherein the multi-head initiator is The catalyst is a composite catalyst of triethyl boron and diphenylboric acid in a molar ratio of 3.0:1; the reaction temperature is increased to 65°C and the polymerization reaction is carried out for 7 hours;

[0125] 2) Add AGE into the kettle, step 1) the molar ratio of propylene oxide to AGE is 100:130, introduce carbon dioxide until the pressure reaches 3.0MPa, and carry out polymerization reaction at 45°C for 12 hours; after the reaction is complete, terminate the reaction to obtain a glue solution; the glue solution is washed and devolatilized to obtain. The number average molecular weight of the obtained copolymer is 40W according to nuclear magnetic resonance detection, of which the molar percentage of the PE rigid segment polymerized by propylene oxide and phthalic anhydride is 43.5%, and the molar percentage of the polycarbonate flexible segment polymerized by AGE and CO2 is 56.5%.

[0126] Preparation of polycarbonate plasticizer F

[0127] 1) Propylene oxide, phthalic anhydride, catalyst and multi-head initiator are placed in a high pressure reactor in a molar ratio of 100:100:0.01:0.105, wherein the multi-head initiator is The catalyst is a composite catalyst of triethyl boron and diphenylboric acid in a molar ratio of 3.0:1; the reaction temperature is increased to 75°C and the polymerization reaction is carried out for 5 hours;

[0128] 2) Add BGE into the kettle, step 1) the molar ratio of propylene oxide to BGE is 100:120, introduce carbon dioxide until the pressure reaches 4.0MPa, and carry out polymerization reaction at 40°C for 15 hours; after the reaction is complete, terminate the reaction to obtain a glue solution; the glue solution is washed and devolatilized to obtain. The number average molecular weight of the obtained copolymer is 36W according to nuclear magnetic resonance detection, of which the molar percentage of the polycarbonate flexible segment of AGE and CO2 is 45.5%, and the molar percentage of the PE rigid segment polymerized by propylene oxide and phthalic anhydride is 56.5%.

[0129] Preparation of polycarbonate plasticizer G

[0130] 1) Ethylene oxide, phthalic anhydride, catalyst and multi-head initiator are put into a high pressure reactor in a molar ratio of 100:100:0.01:7.5, wherein the multi-head initiator is The catalyst is a composite catalyst of triethyl boron and diphenylboric acid in a molar ratio of 3.0:1; the reaction temperature is increased to 55°C and the polymerization reaction is carried out for 4 hours;

[0131] 2) Add AGE into the kettle, step 1) the molar ratio of ethylene oxide to AGE is 100:150, introduce carbon dioxide until the pressure reaches 2.5MPa, and carry out polymerization reaction at 50°C for 3 hours; after the reaction is complete, terminate the reaction to obtain a glue solution; the glue solution is washed and devolatilized to obtain. The number average molecular weight of the obtained copolymer is 8000 as determined by nuclear magnetic resonance, of which the molar percentage of the polycarbonate flexible segment of AGE and CO2 is 40.3%, and the molar percentage of the PE rigid segment polymerized by propylene oxide and phthalic anhydride is 59.7%.

[0132] Preparation of polycarbonate plasticizer H

[0133] 1) Propylene oxide, phthalic anhydride, catalyst and multi-head initiator are placed in a high pressure reactor in a molar ratio of 100:100:0.01:0.138, wherein the multi-head initiator is The catalyst is a composite catalyst of triethyl boron and diphenylboric acid in a molar ratio of 1:3; the reaction temperature is increased to 65°C and the polymerization reaction is carried out for 7 hours;

[0134] 2) Add AGE into the kettle, step 1) the molar ratio of propylene oxide to AGE is 100:130, introduce carbon dioxide until the pressure reaches 3.0MPa, and carry out polymerization reaction at 45°C for 12 hours; after the reaction is complete, terminate the reaction to obtain a glue solution; the glue solution is washed and devolatilized to obtain. The number average molecular weight of the obtained copolymer is 34W according to nuclear magnetic resonance detection, of which the molar percentage of the PE rigid segment polymerized by propylene oxide and phthalic anhydride is 43.9%, and the molar percentage of the polycarbonate flexible segment polymerized by AGE and CO2 is 56.1%.

[0135] Preparation of ABA-structured linear block structure polycarbonate toughening modifier A

[0136] 1) Cyclohexene oxide, triethyl boron and tetra-n-butyl ammonium bromide were added into a high-pressure reactor at a molar ratio of 50:0.01:0.09; carbon dioxide was introduced until the pressure reached 3.5 MPa, the reaction temperature was controlled at 45°C, and the polymerization reaction was carried out for 3 hours;

[0137] 2) After nitrogen substitution in the reactor, propylene oxide was added, the molar ratio of propylene oxide to cyclohexyl oxide in step 1) was 135:50, and the temperature was raised to 65° C. and the polymerization reaction was continued for 10 hours;

[0138] 3) After nitrogen replacement in the reactor, cyclohexene oxide is added, and the molar ratio of cyclohexene oxide to cyclohexene oxide in step 1) is 1:1; and carbon dioxide is introduced until the pressure reaches 3.5MPa, the reaction temperature is reduced to 45°C, and the polymerization reaction is carried out for 4 hours; after the reaction is complete, the reaction is terminated to obtain a glue solution; the glue solution is washed and devolatilized to obtain. The number average molecular weight of the obtained copolymer is 24W according to nuclear magnetic resonance detection, wherein the molar percentage of the polycarbonate rigid segment of cyclohexene oxide and CO2 is 42.5%, and the molar percentage of the PPO flexible segment is 57.5%.

[0139] Preparation of AB-structured linear block structure polycarbonate toughening modifier B

[0140] 1) Cyclohexene oxide, triethylborane and tetra-n-butylammonium bromide were placed in a high-pressure reactor at a molar ratio of 100:0.01:0.09; carbon dioxide was introduced until the pressure reached 3.5 MPa, the reaction temperature was controlled at 45°C, and the polymerization reaction was carried out for 7 hours;

[0141] 2) After nitrogen replacement in the reactor, propylene oxide is added, and the molar ratio of propylene oxide to cyclohexene oxide in step 1) is 135:100. After the temperature is raised to 65°C, the polymerization reaction is continued for 10 hours; after the reaction is complete, the reaction is terminated to obtain a glue solution; the glue solution is washed and devolatilized to obtain a copolymer. The number average molecular weight of the obtained copolymer is 24W according to nuclear magnetic resonance detection, wherein the molar percentage of the polycarbonate rigid segment of cyclohexene oxide and CO2 is 42.5%, and the molar percentage of the PPO flexible segment is 57.5%.

[0142] In order to reflect the effects of different polycarbonate type impact resisters, polycarbonate type plasticizers and their addition amounts in the examples, the additives used in the examples are only symbolically added with 5 parts of UV-1: the chemical name is N-(ethoxycarbonylphenyl)-N'-methyl-N'-phenylformamidine. In actual use, various additives can be added according to the needs of the use environment, and no more examples are given here. The PVC used in the examples is all SG3 type, and the effects of polycarbonate type modifiers on the performance of other PVC types are similar, and no more examples are given here.

[0143] Example 1

[0144] 40 parts by weight of a linear block structure polycarbonate toughening modifier A, M n10 parts by weight of 5000 PC and 5 parts by weight of UV-1 were respectively added into 100 parts by weight of SG3 type PVC for blending to obtain a blended material.

[0145] Example 2

[0146] 40 parts by weight of a linear block structure polycarbonate toughening modifier A, M n 5 parts by weight of 5000 PC and 5 parts by weight of UV-1 were respectively added into 100 parts by weight of SG3 type PVC for blending to obtain a blended material.

[0147] Example 3

[0148] 40 parts by weight of a linear block structure polycarbonate toughening modifier A, M n 20 parts by weight of 5000 PC and 5 parts by weight of UV-1 were added into 100 parts by weight of SG3 type PVC for blending to obtain a blended material.

[0149] Example 4

[0150] 40 parts by weight of a linear block structure polycarbonate toughening modifier A and 5 parts by weight of UV-1 were respectively added into 100 parts by weight of SG3 type PVC for blending to obtain a blended material.

[0151] Example 5

[0152] 40 parts by weight of a linear block structure polycarbonate toughening modifier B, M n 10 parts by weight of 5000 PC and 5 parts by weight of UV-1 were respectively added into 100 parts by weight of SG3 type PVC for blending to obtain a blended material.

[0153] Example 6

[0154] 5 parts by weight of polycarbonate type impact resistant agent A, 35 parts by weight of polycarbonate type plasticizer A, and M n 10 parts by weight of 5000 PC and 5 parts by weight of UV-1 were respectively added into 100 parts by weight of SG3 type PVC for blending to obtain a blended material.

[0155] Example 7

[0156] 5 parts by weight of polycarbonate type impact resistant agent B, 35 parts by weight of polycarbonate type plasticizer B, and M n 10 parts by weight of 5000 PC and 5 parts by weight of UV-1 were respectively added into 100 parts by weight of SG3 type PVC for blending to obtain a blended material.

[0157] Example 8

[0158] 5 parts by weight of polycarbonate type impact resistant agent C, 35 parts by weight of polycarbonate type plasticizer C, n 10 parts by weight of 5000 PC and 5 parts by weight of UV-1 were respectively added into 100 parts by weight of SG3 type PVC for blending to obtain a blended material.

[0159] Example 9

[0160] 5 parts by weight of polycarbonate type impact resistant agent D, 35 parts by weight of polycarbonate type plasticizer D, M n 10 parts by weight of 5000 PC and 5 parts by weight of UV-1 were respectively added into 100 parts by weight of SG3 type PVC for blending to obtain a blended material.

[0161] Example 10

[0162] 5 parts by weight of polycarbonate type impact resistant agent E, 35 parts by weight of polycarbonate type plasticizer E, and M n 10 parts by weight of 5000 PC and 5 parts by weight of UV-1 were respectively added into 100 parts by weight of SG3 type PVC for blending to obtain a blended material.

[0163] Embodiment 11

[0164] 5 parts by weight of polycarbonate type impact resistant agent F, 35 parts by weight of polycarbonate type plasticizer F, and M n 10 parts by weight of 5000 PC and 5 parts by weight of UV-1 were respectively added into 100 parts by weight of SG3 type PVC for blending to obtain a blended material.

[0165] Example 12

[0166] 3 parts by weight of polycarbonate type impact resistant agent G, 7 parts by weight of polycarbonate type plasticizer G, and M n 10 parts by weight of 5000 PC and 5 parts by weight of UV-1 were respectively added into 100 parts by weight of SG3 type PVC for blending to obtain a blended material.

[0167] Embodiment 13

[0168] 10 parts by weight of polycarbonate type impact resistant agent H, 40 parts by weight of polycarbonate type plasticizer H, and M n 10 parts by weight of 5000 PC and 5 parts by weight of UV-1 were respectively added into 100 parts by weight of SG3 type PVC for blending to obtain a blended material.

[0169] The impact resistance and plasticizing properties of the blended materials were tested. The migration property was determined by immersing the PVC material in a food simulating liquid (n-hexane) for 30 days and then measuring the content of the impact agent and plasticizer in the food simulating liquid. The sample T was measured according to GB / T5470-1985. b, the test results are shown in Table 1.

[0170] Table 1

[0171] .

[0172] The above is only a preferred embodiment of the present invention, and does not limit the present invention in other forms. Any technician familiar with the profession may use the above disclosed technical content to change or modify it into an equivalent embodiment with equivalent changes. However, any simple modification, equivalent change and modification made to the above embodiment according to the technical essence of the present invention without departing from the technical solution of the present invention still belongs to the protection scope of the technical solution of the present invention.

Claims

1. An environmentally friendly macromolecular modifier PVC composition, characterized in that: The composition by weight includes: 100 parts of PVC, 1-50 parts of polycarbonate toughening modifier, and 0-30 parts of auxiliary agent. The polycarbonate toughening modifier is a block structure including a rigid segment and a flexible segment. The rigid segment A is a PE segment polymerized by epoxy compound and cyclic acid anhydride or / and a polycarbonate segment of cyclohexene oxide and CO2; the flexible segment B is one or more of a polycarbonate segment of a long-chain epoxy compound and carbon dioxide, a self-polymerized segment of a long-chain epoxy compound, or PPO, and the long-chain epoxy compound is a C4-C20 epoxy compound.

2. An environmentally friendly macromolecular modifier PVC composition according to claim 1, characterized in that: The polycarbonate toughening modifier is a linear block structure.

3. An environmentally friendly macromolecular modifier PVC composition according to claim 2, characterized in that: The linear block structure is a molecular chain in which a rigid segment A and a flexible segment B are connected to form an ABA-type block structure.

4. The environmentally friendly macromolecular modifier PVC composition according to claim 1, characterized in that: The polycarbonate toughening modifier includes the following structure: A n —C, wherein A is a polycarbonate chain, n is 2 to 4, and C is a multi-head initiator residue; the polycarbonate chain is a block structure of a flexible segment and a rigid segment.

5. The environmentally friendly macromolecular modifier PVC composition according to claim 1, characterized in that: The auxiliary agent comprises 0-20 parts by weight of a processing lubricant and 0-10 parts by weight of a heat stabilizer.

6. The environmentally friendly macromolecular modifier PVC composition according to claim 1, characterized in that: The processing lubricant is polypropylene carbonate.