CN107056611A - A kind of reactive plasticizer, its preparation method and the application of polyesters compound - Google Patents
A kind of reactive plasticizer, its preparation method and the application of polyesters compound Download PDFInfo
- Publication number
- CN107056611A CN107056611A CN201710208182.5A CN201710208182A CN107056611A CN 107056611 A CN107056611 A CN 107056611A CN 201710208182 A CN201710208182 A CN 201710208182A CN 107056611 A CN107056611 A CN 107056611A
- Authority
- CN
- China
- Prior art keywords
- plasticizer
- activeness
- quietness
- pbat
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- DQIGFEWVGQCCTN-UHFFFAOYSA-N OC(CO1)COC1=O Chemical compound OC(CO1)COC1=O DQIGFEWVGQCCTN-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C233/09—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to carbon atoms of an acyclic unsaturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C327/00—Thiocarboxylic acids
- C07C327/02—Monothiocarboxylic acids
- C07C327/04—Monothiocarboxylic acids having carbon atoms of thiocarboxyl groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C327/10—Monothiocarboxylic acids having carbon atoms of thiocarboxyl groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an acyclic unsaturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/54—Acrylic acid esters; Methacrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/52—Esters of acyclic unsaturated carboxylic acids having the esterified carboxyl group bound to an acyclic carbon atom
- C07C69/533—Monocarboxylic acid esters having only one carbon-to-carbon double bond
- C07C69/56—Crotonic acid esters; Vinyl acetic acid esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
- C07C69/732—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids of unsaturated hydroxy carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/109—Esters; Ether-esters of carbonic acid, e.g. R-O-C(=O)-O-R
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2312/00—Crosslinking
- C08L2312/06—Crosslinking by radiation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of reactive plasticizer, its preparation method and the application of polyesters compound, ester bond containing polarized and carbon-carbon double bond in the plasticizer.It ensure that plasticizer molecule and PBAT have good compatibility containing ester bond, and the plasticizer with ester bond can produce very strong active force with PBAT strands, produce higher plasticization effect, reduce processing temperature.And by adding this plasticizer with ester bond, it is possible to increase the barrier property of polyester.Plasticizer proposed by the present invention also contains double bond, by adding this kind of plasticizer of certain content among polyesters compound, pass through the post processing means such as ultraviolet light or electron beam irradiation, it can make occur polymerisation between double bond, three-dimensional network is formed in the polyester, increase the entanglement between strand, mechanical property is improved, while also improving its elongation at break.
Description
Technical field
The invention belongs to material processing field, more particularly, to a kind of response type of activeness and quietness polyesters compound
Plasticizer, its preparation method and application.
Background technology
Aliphatic-aromatic copolyester has good biological degradability, and heat endurance is good, good mechanical performance, significantly
The performance of original aliphatic polyester is improved, there is good application prospect in future.PBAT is used as such petchem
Represent, its tensile strength is in more than 20MPa, and extension at break can reach 500%, excellent combination property, but PBAT is as can
Biodegradation material, it is narrower to face processing temperature scope when processing, the problem of temperature is higher.And the fracture of PBAT films
Elongation is not high enough, adds its mechanical properties decrease after additive, the problem of easily occurring in terms of tearing.In addition,
PBAT films are due to being that the ester bond of polarity is connected, and barrier property is not very excellent.Especially in agriculture field, it is necessary to
Film has higher water retention property, therefore faces many problems above in application.The problem of to solve this respect, it can add
Add barrier when work into PBAT, such as the water preventing ability material such as organo montmorillonite.But pass through additive barrier
The method of matter can bring processing price high, product properties decline, the shortcoming in terms of translucency difference.
The content of the invention
For the disadvantages described above or Improvement requirement of prior art, the invention provides a kind of activeness and quietness polyesters compound
Reactive plasticizer, its preparation method and application, it is a kind of containing ester bond and double its object is to be prepared by chemical synthesis
The plasticizer of key, by adding the plasticizer into polyester, makes polyester have more preferable processing characteristics, and improve its extension at break
Rate, simultaneously because containing double bond in the plasticizer, after irradiated processing, can significantly improve the mechanical property of polyester, thus solve
Certainly the aliphatic-aromatic copolyester of prior art such as PBAT processing difficulties, barrier is bad, after additive is added under mechanical property
Drop, easily tear；The technical problem that obstructs after additive is added that translucency is bad, cost is high etc..
To achieve the above object, according to one aspect of the present invention, there is provided a kind of reactive plasticizer, the plasticizer
Contain ester bond and carbon-carbon double bond.
Preferably, the plasticizer has the structure as shown in formula (one) or formula (two)：
Wherein, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12And R13Be each independently H, C1-C20 alkyl,
The C1-C20 of C1-C20 alkoxy, halogen or amino substitution alkyl, the alkoxy of halogen or the C1-C20 of amino substitution or
Halogenated hydrocarbons；Y is O, S, or NH；M and n is each independent natural number, it is preferable that m, n are respectively 0~18 natural number.
Preferably, the plasticizer has the molecular structure as shown in formula (three), formula (four), formula (five) or formula (six)
According to another aspect of the present invention there is provided a kind of preparation method of described plasticizer, double bond will be contained
Carboxylic acid or anhydride chloride obtain chloride compounds, and with alcohol compound esterification occurs for the chloride compounds.
According to another aspect of the present invention there is provided a kind of application of described plasticizer, applied to polyesters chemical combination
The activeness and quietness of thing.
Preferably, when the plasticizer is applied to the activeness and quietness of polyesters compound, the quality of the plasticizer is added
Fraction is 1%~50%.
Preferably, the mass fraction for adding the plasticizer is 1%~30%.
According to another aspect of the present invention there is provided a kind of activeness and quietness method of polyesters compound, including it is as follows
Step：
(1) described plasticizer is well mixed with polyesters compound, obtains mixture, increased described in the mixture
The mass percent for moulding agent is 1%~50%.
Preferably, described activeness and quietness method, in addition to step：
(2) mixture obtained using ultraviolet light or electron beam irradiation step (1), that is, obtained after activeness and quietness
Polyester.
When preferably, using the ultraviolet light, the wave-length coverage of ultraviolet light is 100~300nm, and irradiation time is 1
~50min.
When preferably, using the electron beam irradiation, the intensity of electron beam irradiation is 20~200kGy, and exposure time is 1
~20min.
According to another aspect of the present invention there is provided a kind of PBAT polyester of activeness and quietness, the activeness and quietness
It is the plasticizer described in 1%~50% that PBAT polyester, which includes mass fraction, and the plasticizer is used to carry out the PBAT polyester
Activeness and quietness.
Preferably, the PBAT polyester of described activeness and quietness, compared with pure PBAT polyester, the PBAT of the activeness and quietness gathers
The tensile strength of ester improves 5.4%~40.8%, and elongation at break improves 13.3%~130.5%
In general, by the contemplated above technical scheme of the present invention compared with prior art, it can obtain down and show
Beneficial effect.
(1) present invention proposes a kind of ester bond containing polarized and the plasticizer of double bond, and plasticising is ensure that containing ester bond
Agent molecule has good compatibility with PBAT, and the plasticizer with ester bond can produce very strong effect with PBAT strands
Power, produces higher plasticization effect, reduces processing temperature.And by adding this plasticizer with ester bond, it is possible to increase
The barrier property of polyester.
(2) plasticizer proposed by the present invention also contains double bond, by adding this kind of plasticizer of certain content to polyesters
Among compound, by the post processing means such as ultraviolet light or electron beam irradiation, it can make occur polymerisation between double bond,
The entanglement formed in polyester between three-dimensional network, increase strand, improves mechanical property, while also improving its extension at break
Rate.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.As long as in addition, technical characteristic involved in each embodiment of invention described below each other it
Between do not constitute conflict can just be mutually combined.
It is used for polyester the invention provides one kind and is plasticized enhanced reactive plasticizer, its ester bond containing polarized and carbon carbon is double
Key, such as the structure as shown in formula (one) or formula (two)
Wherein, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12And R13Be each independently H, C1-C20 alkyl,
The C1-C20 of C1-C20 alkoxy, halogen or amino substitution alkyl, the alkoxy of halogen or the C1-C20 of amino substitution or
Halogenated hydrocarbons；Y is O, S, or NH；M and n are each independently natural number, it is preferable that m, n are each independently 0~18 nature
Number.
It is preferred that molecular structure of the plasticizer as shown in formula (three), formula (four), formula (five) and formula (six)：
The preparation method for the plasticizer that the present invention is provided, can be by the way that carboxylic acid or anhydride chloride containing double bond be obtained
To chloride compounds, it is that can obtain that then with alcohol compound esterification, which occurs, for chloride compounds.
The preparation method of wherein chloride compounds is：By the amount ratio of carboxylic acid and thionyl chloride containing double bond according to material
For 1:After 5 is well mixed, 4~6h is reacted at 90 DEG C in the presence of catalyst, described chloride compounds are obtained.
Carboxylic acid containing double bond is such as：Acrylic acid or the molecule as shown in formula (seven), formula (eight) or formula (nine)：
Alcohol compound includes monohydric alcohol, unitary mercaptan, alkylamine or the lactone containing hydroxyl；Monohydric alcohol such as first
Alcohol, ethanol or isopropanol；Unitary mercaptan such as ethyl mercaptan；Alkylamine such as n-butylamine.
Specifically, for the plasticizer shown in formula (one), it can be prepared via a method which to obtain：
(1) carboxylic acid containing double bond, such as acrylic acid, 2- butenoic acids are utilized, and (structural formula is such as the butenoic acid of 4- hydroxyls -2
Shown in formula (three)) flowed back with thionyl chloride in the presence of catalyst at 90 DEG C 4~6h, obtain chloride compounds, wherein carboxylic acid
Ratio with thionyl chloride is 1：5；
(2) compounds such as chloride compounds and monohydric alcohol/unitary mercaptan/alkylamine are reacted, such compound can be
Methanol, ethanol, isopropanol, ethyl mercaptan, n-butylamine etc., prepare the plasticizer shown in formula (one), wherein acyl chlorides and monohydric alcohol
Ratio be 1：1, reaction temperature is 80 DEG C, and the reaction time is 12h, backflow, inert gas shielding.
For the plasticizer shown in formula (two), it can be prepared using following preparation method：
(1) carboxylic acid containing double bond, such as three kinds of carboxylic acids as shown in formula (four), formula (five), formula (six), with chlorination are utilized
Sulfoxide, in the 6h that flowed back at 90 DEG C, obtains chloride compounds, the ratio of wherein carboxylic acid and thionyl chloride is in the presence of catalyst
1:5；
(2) trihydroxylic alcohol flows back with dimethyl carbonate under the conditions of 80 DEG C, obtains the lactone containing hydroxyl；Wherein trihydroxylic alcohol can
Think glycerine, using tetrahydrofuran as solvent, reaction temperature is 80 DEG C, backflow；The amount ratio of trihydroxylic alcohol and dimethyl carbonate material
Example is 1:1.
(3) it is 1 according to the amount ratio of material by chloride compounds and the lactone containing hydroxyl:1, under inert gas shielding
80 DEG C of back flow reaction 30h, obtain target product.
The plasticizer that the present invention is provided can be applied to the activeness and quietness of polyesters compound, including increase the polyesters
The tensile strength and elongation at break of compound.
By the present invention plasticizer with 1~50wt%, be especially added to 1~30wt% in polyester, such as gather oneself two
When in acid/butylene terephthalate (PBAT), polybutylene terephthalate (PBT) (PBT), plasticising effect well can be produced
Really；Post-processed by methods such as ultraviolet light or electron beam irradiations, its mechanical strength also has with elongation at break
Very big lifting.
Present invention provides a kind of activeness and quietness method of polyesters compound, comprise the following steps：
(1) plasticizer of the present invention is well mixed with polyesters compound, mixture is obtained, described in the mixture
The mass percent of plasticizer is 1%~50%.
(2) mixture obtained using ultraviolet light or electron beam irradiation step (1), that is, obtained after activeness and quietness
Polyester.
During using the ultraviolet light, the wave-length coverage of ultraviolet light is preferably 100~300nm, and irradiation time is preferably 1
~50min；
During using the electron beam irradiation, the intensity of electron beam irradiation is preferably 20~200kGy, and exposure time is preferably 1
~20min.
The enhanced processing method of toughness reinforcing, bag are carried out to polyester present invention also offers the reactive plasticizer using the present invention
Include following steps：
(1) described reactive plasticizer is well mixed with polyester, then granulated by single screw extrusion machine, mixed
Compound, the mass percent of plasticizer described in the mixture is 1%~50%；Mixture is added by double screw extruder
Work, is made product；
The processing method that this kind of plasticizer that the present invention is provided is added in polyesters compound solves prior art and is
To improve defect of the polyesters compound in processing in terms of the excessively high processing of processing temperature.But only by plasticizer with gathering
Ester type compound mixing is merely capable of improving the elongation at break of material, and mechanical property declines on the contrary.To solve under mechanical property
The problem of drop, the present invention also add post-processing step, post-processing approach preferably is such as using the double bond contained in plasticizer
Under：
(2) product obtained using ultraviolet light or electron beam irradiation step (1), that is, obtain poly- after enhancing plasticising
Ester.
During using the ultraviolet light, the wave-length coverage of ultraviolet light is 100~300nm, and irradiation time is 1~50min；
During using the electron beam irradiation, the intensity of electron beam irradiation is 20~200kGy, and exposure time is 1~20min.
A kind of polyester of new activeness and quietness can be prepared using the plasticizer and activeness and quietness method of the present invention
Class compound, it includes mass fraction for 1%~50% plasticizer of the present invention, and the plasticizer is used for the polyesters
Compound such as PBAT or PBT carry out activeness and quietness.This new polyesters compound and existing polyesters compound phase ratio, tool
There is more excellent mechanical strength and elongation at break.
The such as embodiment of the present invention 14 is using the elasticizer plasticizing PBAT shown in formula (three), when plasticizer loading is 5%,
Its elongation at break improves 170.5%, draws high intensity by reduction by 7.9%；In the radiation treatment 5min of 30kGy intensity, its mechanics
Intensity improves 18.7%, and elongation at break improves 125.4%.
The PBAT polyester for the activeness and quietness that the present invention is provided, compared with pure PBAT polyester, its tensile strength improves 5.4%
~40.8%, elongation at break improves 13.3%~130.5%
The present invention proposes the plasticizer of a kind of ester bond containing polarized and carbon-carbon double bond.And the polyesters compound such as PBAT
Contain substantial amounts of ester bond in molecular structure, so ensure that plasticizer and PBAT compatibility.And the plasticising with ester bond
Agent can produce very strong active force with PBAT strands, produce higher plasticization effect, reduce processing temperature.And by adding
Plus this plasticizer with ester bond, barrier property can be improved to a certain extent.
But add the decline that the another question that faces of plasticizer is mechanical property.For the problem, the present invention exists
Introduce on the basis of ester bond, synthesized the plasticizer with double bond structure.By adding this kind of plasticizer of certain content to poly-
Among ester type compound, then by the post processing means such as ultraviolet light or electron beam irradiation, it can make to occur to gather between double bond
Reaction is closed, the crosslinking and entanglement formed in the polyester between three-dimensional network, increase strand improves mechanical property.While its
Elongation at break, which also has, to be improved.
It is embodiment below：
Embodiment 1
A kind of preparation method of the reactive plasticizer of polyester, is carried out in accordance with the following steps：
7.2g acrylic acid is added in 250mL round-bottomed flasks, 36mL thionyl chlorides is then added, is used under the conditions of 90 DEG C
Serpentine condenser back flow reaction 6h.After reaction terminates, excessive thionyl chloride is first distilled out with Rotary Evaporators at 35 DEG C, so
Rear pump or output pump vacuum distillation under the conditions of 40 DEG C obtains 8.64g acryloyl chlorides, and the conversion ratio of acrylic acid is 83%.Then by acryloyl
Chlorine 8.64g and 2.66g methanol back flow reaction 12h under the conditions of 60 DEG C, obtains plasticizer methyl acrylate (being shown below).
Embodiment 2
A kind of preparation method of the reactive plasticizer of polyester, is carried out in accordance with the following steps：
8.6g 2- butenoic acids are added in 250mL round-bottomed flasks, 36mL thionyl chlorides are then added, in 90 DEG C of conditions
Lower use serpentine condenser back flow reaction 6h.After reaction terminates, excessive protochloride is first distilled out with Rotary Evaporators at 35 DEG C
Sulfone, then oil pump vacuum distillation under the conditions of 40 DEG C obtains 7.95g2- crotonyl chlorides, and the conversion ratio of 2- butenoic acids is 76%.So
Afterwards by methacrylic chloride 7.95g and 3.50g ethanol back flow reaction 12h under the conditions of 60 DEG C, plasticizer 2- butenoic acid first is obtained
Ester (is shown below).
Embodiment 3
A kind of preparation method of the reactive plasticizer of polyester, is carried out in accordance with the following steps：
The butenoic acid of 10.2g 4- hydroxyls -2 will be added in 250mL round-bottomed flasks, and then add 36mL thionyl chlorides,
Serpentine condenser back flow reaction 6h is used under the conditions of 90 DEG C.After reaction terminates, first excess is distilled out with Rotary Evaporators at 35 DEG C
Thionyl chloride, then oil pump vacuum distillation under the conditions of 40 DEG C obtains the crotonyl chloride of 8.196g4- hydroxyls -2, the fourth of 4- hydroxyls -2
The conversion ratio of olefin(e) acid is 68%.Then the crotonyl chloride 8.196g of 4- hydroxyls -2 and 4.087g isopropanols are flowed back under the conditions of 60 DEG C
12h is reacted, the butylene isopropyl propionate (being shown below) of plasticizer 4- hydroxyls -2 is obtained.
Embodiment 4
A kind of preparation method of the reactive plasticizer of polyester, is carried out in accordance with the following steps：
8.6g 2- butenoic acids are added in 250mL round-bottomed flasks, 36mL thionyl chlorides are then added, in 90 DEG C of conditions
Lower use serpentine condenser back flow reaction 6h.After reaction terminates, excessive protochloride is first distilled out with Rotary Evaporators at 35 DEG C
Sulfone, then oil pump vacuum distillation under the conditions of 40 DEG C obtains 7.95g2- crotonyl chlorides, and the conversion ratio of 2- butenoic acids is 76%.So
Afterwards by methacrylic chloride 7.95g and 4.72g ethyl mercaptans back flow reaction 12h under the conditions of 60 DEG C, plasticizer 2- butenoic acids are obtained
Ethyl mercaptan ester (is shown below).
Embodiment 5
A kind of preparation method of the reactive plasticizer of polyester, is carried out in accordance with the following steps：
7.2g acrylic acid is added in 250mL round-bottomed flasks, 36mL thionyl chlorides is then added, is used under the conditions of 90 DEG C
Serpentine condenser back flow reaction 6h.After reaction terminates, excessive thionyl chloride is first distilled out with Rotary Evaporators at 35 DEG C, so
Rear pump or output pump vacuum distillation under the conditions of 40 DEG C obtains 8.64g acryloyl chlorides, and the conversion ratio of acrylic acid is 83%.Then by acryloyl
Chlorine 8.64g and 6.31g n-butylamines back flow reaction 12h under the conditions of 60 DEG C, obtains acrylic acid n-butylamine ester (being shown below).
Embodiment 6
A kind of preparation method of the reactive plasticizer of polyester, is carried out in accordance with the following steps：
11.6g maleic acids (shown in formula (4)) are added in 250mL round-bottomed flasks, 72mL thionyl chlorides are then added,
Serpentine condenser back flow reaction 6h is used under the conditions of 90 DEG C.After reaction terminates, first excess is distilled out with Rotary Evaporators at 35 DEG C
Thionyl chloride, then oil pump vacuum distillation under the conditions of 70 DEG C obtains 12.39g maleic acid diacid chlorides, the conversion ratio of maleic acid
For 81%.
9.2g glycerine and 9.0g dimethyl carbonates, 45mL tetrahydrofurans are added in round-bottomed flask, at 80 DEG C next time
Flow 12h.After reaction terminates, with Rotary Evaporators vacuum distillation at 30 DEG C, 2- hydroxyl trimethylene carbonic esters are obtained.
Then by 2- hydroxyl trimethylene carbonic esters and maleic acid diacid chloride according to mole 2:1 is added in flask, in N2Atmosphere
Enclose lower 80 DEG C of reactions 30h, you can the plasticizer being shown below.
Embodiment 7
A kind of preparation method of the reactive plasticizer of polyester, is carried out in accordance with the following steps：
Compound shown in 12.0g formulas (5) is added in 150mL round-bottomed flasks, 36mL thionyl chlorides are then added,
Serpentine condenser back flow reaction 6h is used under the conditions of 90 DEG C.After reaction terminates, first excess is distilled out with Rotary Evaporators at 35 DEG C
Thionyl chloride, then oil pump vacuum distillation under the conditions of 60 DEG C obtains 11.8g chloride compounds, and conversion ratio is 85%.
9.2g glycerine and 9.0g dimethyl carbonates, 45mL tetrahydrofurans are added in round-bottomed flask, at 80 DEG C next time
Flow 12h.After reaction terminates, with Rotary Evaporators vacuum distillation at 30 DEG C, 2- hydroxyl trimethylene carbonic esters are obtained.
Then by 2- hydroxyl trimethylene carbonic esters and chloride compounds according to mole 1:1 is added in flask, in N2Atmosphere
Lower 80 DEG C of reactions 30h, you can the plasticizer being shown below.
Embodiment 8
A kind of preparation method of the reactive plasticizer of polyester, is carried out in accordance with the following steps：
Compound shown in 8.6g formulas (6) is added in 150mL round-bottomed flasks, 36mL thionyl chlorides are then added,
Serpentine condenser back flow reaction 6h is used under the conditions of 90 DEG C.After reaction terminates, first excess is distilled out with Rotary Evaporators at 35 DEG C
Thionyl chloride, then with oil pump, vacuum distillation obtains 8.8g chloride compounds under the conditions of 55 DEG C, and conversion ratio is 84%.
9.2g glycerine and 9.0g dimethyl carbonates, 45mL tetrahydrofurans are added in round-bottomed flask, at 80 DEG C next time
Flow 12h.After reaction terminates, with Rotary Evaporators vacuum distillation at 30 DEG C, 2- hydroxyl trimethylene carbonic esters are obtained.
Then by 2- hydroxyl trimethylene carbonic esters and chloride compounds according to mole 1:1 is added in flask, in N2Atmosphere
Lower 80 DEG C of reactions 30h, you can the plasticizer being shown below.
Embodiment 9
One kind carries out the enhanced processing method of plasticising to PBAT using methyl acrylate, carries out in accordance with the following steps：
According to mass ratio it is 99 by PBAT and methyl acrylate:1 stirs in high mixer, is then added to single screw rod
Extruding pelletization in extruder, and obtained compound particles are dried in an oven.Finally dried mixture is added to
In double screw extruder, dumbbell shaped batten is made by mould.The dumbbell shaped batten being made is divided into three groups, labeled as A, B, C.
A groups are without any post processing, and B groups irradiate 1min under the ultraviolet light of 100nm wavelength, and C groups are in 300nm wavelength
50min is irradiated under ultraviolet light.
This three groups of battens are done into tension test respectively, compared with A groups, the tensile strength rise 21.4% of B group battens is broken
Split elongation rise 38.9%；The tensile strength rise 33.5% of C group battens, elongation at break rise 13.3%.
Embodiment 10
The plasticizer (being shown below) prepared using embodiment 4 carries out plasticising enhancing to PBT, as follows
Carry out：
The plasticizer that embodiment 4 is made is with PBT using mass ratio as 50:Stir, be then added in 50 high mixers
Extruding pelletization in single screw extrusion machine, and obtained compound particles are dried in an oven.Finally by dried mixture
It is added in double screw extruder, dumbbell shaped batten is made by mould.The dumbbell shaped batten being made is divided into three groups of groups, marked
For A, B, C.
A groups irradiate 20min without any post processing, B groups in the case where irradiation intensity is 20kGy electron beam, and C groups are in intensity
To irradiate 1min under 200kGy electron beam.
This two groups of battens are done into tension test respectively, compared with pure PET battens A, the tensile strength rise of B group battens
23.5%, elongation at break rise 25.7%；The tensile strength rise 27.9% of C group battens, elongation at break rise 34.5%.
Embodiment 11
The plasticizer (being shown below) prepared using embodiment 8 carries out plasticising enhancing to PBAT, according to such as lower section
Method is carried out：
The plasticizer that embodiment 8 is made is with PBAT using mass ratio as 50:Stir, be then added in 50 high mixers
Extruding pelletization in single screw extrusion machine, and obtained compound particles are dried in an oven.Finally by dried mixture
It is added in double screw extruder, dumbbell shaped batten is made by mould.The dumbbell shaped batten being made is divided into three groups of groups, marked
For A, B, C.
A groups irradiate 10min without any post processing, B groups in the case where irradiation intensity is 80kGy electron beam, and C groups are in intensity
To irradiate 5min under 200kGy electron beam.
This three groups of battens are done into tension test respectively, compared with A groups, the tensile strength rise 40.8% of B group battens is broken
Split elongation rise 117.5%；The tensile strength rise 53.2% of C group battens, elongation at break rise 80.5%.
Embodiment 12
The plasticizer (being shown below) prepared using embodiment 5 carries out plasticising enhancing to PBAT, according to such as lower section
Method is carried out：
The plasticizer that embodiment 5 is made is with PBAT using mass ratio as 10:Stir, be then added in 90 high mixers
Extruding pelletization in single screw extrusion machine, and obtained compound particles are dried in an oven.Finally by dried mixture
It is added in double screw extruder, dumbbell shaped batten is made by mould.The dumbbell shaped batten being made is divided into two groups, is labeled as
A、B。
A groups irradiate 10min without any post processing, B groups in the case where irradiation intensity is 80kGy electron beam.By this three groups
Batten does tension test respectively, compared with A groups, the tensile strength rise 10.4% of B group battens, elongation at break rise
130.5%.
Increase respectively to not adding the pure PBAT of plasticizer, adding the not post-treated PBAT (A groups) of plasticizer and add
PBAT (B groups) after modeling agent and radiation treatment carries out infrared test respectively, and obtained infrared spectrum shows, adds plasticizer and warp
Later (wave number is in 1641cm at the peak of the B group PBAT double bonds after handling-1Place) disappear substantially.
Embodiment 13
The plasticizer prepared using embodiment 5 carries out plasticising enhancing to PBAT, carries out as follows：
The plasticizer that embodiment 5 is made is with PBAT using mass ratio as 20:Stir, be then added in 80 high mixers
Extruding pelletization in single screw extrusion machine, and obtained compound particles are dried in an oven.Finally by dried mixture
It is added in double screw extruder, dumbbell shaped batten is made by mould.The dumbbell shaped batten being made is divided into two groups, is labeled as
A、B。
A groups irradiate 5min without any post processing, B groups in the case where irradiation intensity is 50kGy electron beam.
Compared to pure PBAT, A group battens elongation at break improves 124.3%, and tensile strength declines 15.2%；B group battens
Elongation at break improves 81.2%, and tensile strength improves 13.4%.
Embodiment 14
The plasticizer prepared using embodiment 5 carries out plasticising enhancing to PBAT, carries out as follows：
The plasticizer that embodiment 5 is made is with PBAT using mass ratio as 5:Stir, be then added in 95 high mixers
Extruding pelletization in single screw extrusion machine, and obtained compound particles are dried in an oven.Finally by dried mixture
It is added in double screw extruder, dumbbell shaped batten is made by mould.
Mechanics Performance Testing is carried out to batten, its elongation at break improves 170.5%, tensile strength reduction by 7.9%；
The radiation treatment 5min of 30kGy intensity, tensile strength improves 18.7%, and elongation at break improves 125.4%.
Embodiment 15
The plasticizer (shown in following schema) prepared using embodiment 7 carries out plasticising enhancing to PBAT, according to as follows
Method is carried out：
The plasticizer that embodiment 7 is made is with PBAT using mass ratio as 10:Stir, be then added in 90 high mixers
Extruding pelletization in single screw extrusion machine, and obtained compound particles are dried in an oven.Finally by dried mixture
It is added in double screw extruder, dumbbell shaped batten is made by mould.The dumbbell shaped batten being made is divided into three groups of groups, marked
For A, B.
A groups irradiate 5min without any post processing, B groups in the case where irradiation intensity is 50kGy electron beam.
Compared to pure PBAT, A group battens elongation at break improves 140.5%, and tensile strength declines 32.4%；B group battens
Elongation at break improves 95.4%, and tensile strength improves 5.4%.
Embodiment 16
The plasticizer (shown in following schema) prepared using embodiment 6 carries out plasticising enhancing to PBAT, according to as follows
Method is carried out：
The plasticizer that embodiment 6 is made is with PBAT using mass ratio as 30:Stir, be then added in 70 high mixers
Extruding pelletization in single screw extrusion machine, and obtained compound particles are dried in an oven.Finally by dried mixture
It is added in double screw extruder, dumbbell shaped batten is made by mould.The dumbbell shaped batten being made is divided into three groups of groups, marked
For A, B.
A groups irradiate 5min without any post processing, B groups in the case where irradiation intensity is 50kGy electron beam.
Compared to pure PBAT, A group battens elongation at break improves 167.8%, and tensile strength declines 45.9%；B group battens
Elongation at break improves 120.6%, and tensile strength improves 8.4%.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, it is not used to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the invention etc., it all should include
Within protection scope of the present invention.
Claims (10)
1. a kind of reactive plasticizer, it is characterised in that the plasticizer contains ester bond and carbon-carbon double bond.
2. plasticizer as claimed in claim 1, it is characterised in that the plasticizer has as shown in formula (one) or formula (two)
Structure：
Wherein, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12And R13It is each independently H, C1-C20 alkyl, C1-
The alkoxy or halo for the C1-C20 that alkyl, halogen or the amino for the C1-C20 that C20 alkoxy, halogen or amino replaces replace
Hydrocarbon；Y is O, S, or NH；M and n is each independent natural number, it is preferable that m, n are each independently 0~18 natural number.
3. plasticizer as claimed in claim 2, it is characterised in that the plasticizer has such as formula (three), formula (four), formula (five)
Or the molecular structure shown in formula (six)
4. the preparation method of a kind of plasticizer as described in claims 1 to 3 any one, it is characterised in that double bond will be contained
Carboxylic acid or anhydride chloride obtain chloride compounds, with alcohol compound esterification occurs for the chloride compounds.
5. the application of a kind of plasticizer as described in claims 1 to 3 any one, it is characterised in that applied to polyesters
The activeness and quietness of compound.
6. application as claimed in claim 6, it is characterised in that the plasticizer is applied to the activeness and quietness of polyesters compound
When, the mass fraction for adding the plasticizer is 1%~50%, preferably 1%~30%.
7. a kind of activeness and quietness method of polyesters compound, it is characterised in that comprise the following steps：
(1) plasticizer as described in claims 1 to 3 any one is well mixed with polyesters compound, obtains mixture,
The mass percent of plasticizer described in the mixture is 1%~50%.
8. activeness and quietness method as claimed in claim 7, it is characterised in that also including step：
(2) mixture obtained using ultraviolet light or electron beam irradiation step (1), that is, obtain poly- after activeness and quietness
Ester；
During using the ultraviolet light, the wave-length coverage of ultraviolet light is preferably 100~300nm, and irradiation time is preferably 1~
50min；
During using the electron beam irradiation, the intensity of electron beam irradiation is preferably 20~200kGy, and exposure time is preferably 1~
20min。
9. a kind of PBAT polyester of activeness and quietness, its spy is, it is 1% that the PBAT polyester of the activeness and quietness, which includes mass fraction,
~50% plasticizer as described in claims 1 to 3 any one, the plasticizer is used to increase the PBAT polyester
Strong toughness reinforcing.
10. the PBAT polyester of activeness and quietness as claimed in claim 10, it is characterised in that described compared with pure PBAT polyester
The tensile strength of the PBAT polyester of activeness and quietness improves 5.4%~40.8%, and elongation at break improves 13.3%~
130.5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710208182.5A CN107056611B (en) | 2017-03-31 | 2017-03-31 | Reactive plasticizer of polyester compound, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710208182.5A CN107056611B (en) | 2017-03-31 | 2017-03-31 | Reactive plasticizer of polyester compound, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107056611A true CN107056611A (en) | 2017-08-18 |
| CN107056611B CN107056611B (en) | 2020-05-19 |
Family
ID=59602703
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710208182.5A Active CN107056611B (en) | 2017-03-31 | 2017-03-31 | Reactive plasticizer of polyester compound, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107056611B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778379A (en) * | 2019-11-07 | 2021-05-11 | 华中科技大学 | Method for synthesizing deuterated compound in aqueous solvent |
| CN113817148A (en) * | 2021-09-14 | 2021-12-21 | 内蒙古农业大学 | Polylactic acid copolymer, preparation method and application thereof, and preparation method of blended film |
| CN114605283A (en) * | 2022-03-22 | 2022-06-10 | 宿迁盛基医药科技有限公司 | Method for efficiently preparing montelukast sodium side chain intermediate |
| CN114605282A (en) * | 2022-03-22 | 2022-06-10 | 宿迁盛基医药科技有限公司 | Preparation method of montelukast sodium side chain intermediate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001192379A (en) * | 1999-10-28 | 2001-07-17 | Mitsubishi Rayon Co Ltd | 1,3-dioxan-2-on-5-yl(meth)acrylate and method for producing the same |
| WO2005016865A1 (en) * | 2003-07-31 | 2005-02-24 | Basf Corporation | Gamma hydroxy carbamate compounds and methods of making and using the same |
| CN1749292A (en) * | 2005-10-18 | 2006-03-22 | 上海昊海化工有限公司 | Single component polyurethane foam of improved surface toughness and its preparing method |
| CN102775593A (en) * | 2012-08-17 | 2012-11-14 | 中国科学院长春应用化学研究所 | Catalyst composite and method for preparing polycarbonate |
-
2017
- 2017-03-31 CN CN201710208182.5A patent/CN107056611B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001192379A (en) * | 1999-10-28 | 2001-07-17 | Mitsubishi Rayon Co Ltd | 1,3-dioxan-2-on-5-yl(meth)acrylate and method for producing the same |
| WO2005016865A1 (en) * | 2003-07-31 | 2005-02-24 | Basf Corporation | Gamma hydroxy carbamate compounds and methods of making and using the same |
| CN1749292A (en) * | 2005-10-18 | 2006-03-22 | 上海昊海化工有限公司 | Single component polyurethane foam of improved surface toughness and its preparing method |
| CN102775593A (en) * | 2012-08-17 | 2012-11-14 | 中国科学院长春应用化学研究所 | Catalyst composite and method for preparing polycarbonate |
Non-Patent Citations (3)
| Title |
|---|
| 350009-13-1: "RN", 《STN REG》 * |
| 周祥兴编: "《中外塑料改性助剂速查手册》", 30 November 2009, 机械工业出版社 * |
| 李红强主编: "《胶粘原理、技术及应用》", 31 January 2014, 华南理工大学出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778379A (en) * | 2019-11-07 | 2021-05-11 | 华中科技大学 | Method for synthesizing deuterated compound in aqueous solvent |
| CN112778379B (en) * | 2019-11-07 | 2022-10-14 | 华中科技大学 | Method for synthesizing deuterated compound in aqueous solvent |
| CN113817148A (en) * | 2021-09-14 | 2021-12-21 | 内蒙古农业大学 | Polylactic acid copolymer, preparation method and application thereof, and preparation method of blended film |
| CN114605283A (en) * | 2022-03-22 | 2022-06-10 | 宿迁盛基医药科技有限公司 | Method for efficiently preparing montelukast sodium side chain intermediate |
| CN114605282A (en) * | 2022-03-22 | 2022-06-10 | 宿迁盛基医药科技有限公司 | Preparation method of montelukast sodium side chain intermediate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107056611B (en) | 2020-05-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107056611A (en) | A kind of reactive plasticizer, its preparation method and the application of polyesters compound | |
| Xiong et al. | Economically competitive biodegradable PBAT/lignin composites: Effect of lignin methylation and compatibilizer | |
| JP6517761B2 (en) | Polymer composition and method | |
| Jasinska et al. | Unsaturated, biobased polyesters and their cross‐linking via radical copolymerization | |
| CN107254002A (en) | Nano-cellulose containing cinnamyl functional groups and its preparation method and application | |
| Wang et al. | Furfural-derived diacid prepared by photoreaction for sustainable materials synthesis | |
| CN1631935A (en) | Synthesis of p-phenyl unsaturated polyester resin by using waste polyester material | |
| CN104072954B (en) | A kind of poly-FDCA glycol ester matrix material and preparation method thereof | |
| CN102731755A (en) | Method for preparing plasticizer | |
| CN1076702A (en) | The polymkeric substance of high side chain and the preparation method of high branched-chain polymer | |
| WO1999010354A1 (en) | Phosphoric ester compounds and process for producing the same, copper phosphoric ester compounds and process for producing the same, near infrared absorber, and near infrared absorbent acrylic resin composition | |
| Wang et al. | Cyclobutane-1, 3-diacid (CBDA): a semi-rigid building block prepared by [2+ 2] photocyclization for polymeric materials | |
| CN1735418A (en) | Micelle assemblies | |
| CN111978444A (en) | Organic polyacid-based photocuring resin and preparation method and application thereof | |
| CN1300213C (en) | Ternary copoly ester capable of biological degradation and its preparation method | |
| CN101298504A (en) | Supermolecule polymer micelle and preparation thereof | |
| CN106432706B (en) | A kind of self-emulsification aqueous polyester emulsion and preparation method thereof | |
| Valentino et al. | Furfuryl alcohol/tung oil matrix-based composites reinforced with bacterial cellulose fibres | |
| Lai et al. | Renewable photopolymers: transformation of biomass resources into value-added products under light | |
| Tsubaki | Synthesis and properties of the chiral oligonaphthalenes | |
| Akae et al. | O‐Acylative Vinylation of Cyclodextrin‐Based [3] Rotaxane Towards Rotaxane Crosslinkers | |
| JPS6058411A (en) | Organopolysiloxane-polyester-vinyl graft copolymer and manufacture | |
| CN101050276A (en) | Polyethyleneglycol of end group of amino acid, and preparation method | |
| TW201434936A (en) | Dispersant for inorganic particle, composition comprising the same, curable composition, cured product and thin film | |
| CN1271141C (en) | Curable resin composition and process for preparing low-polymer containing acrylyl and substituted methacrylic acid radical |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |