CN109705272A - Microspheroidal ionomer with cross-linked structure and its preparation method and application - Google Patents
Microspheroidal ionomer with cross-linked structure and its preparation method and application Download PDFInfo
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- CN109705272A CN109705272A CN201711010202.4A CN201711010202A CN109705272A CN 109705272 A CN109705272 A CN 109705272A CN 201711010202 A CN201711010202 A CN 201711010202A CN 109705272 A CN109705272 A CN 109705272A
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Abstract
The present invention relates to polymeric material field, the microspheroidal ionomer and its preparation method and application with cross-linked structure is disclosed.The preparation method of the ionomer include: (1) in organic solvent, in the presence of first part's initiator, maleic anhydride and first part monomer M contact are reacted, being re-introduced into the solution containing crosslinking agent, the reaction was continued, wherein, it is represented by a formula X to contain crosslinking agent, optional second part monomer M and optional second part initiator, the structure of monomer M for the solution containing crosslinking agent, in Formula X, R is H or methyl；(2) in presence of water, step (1) products therefrom is contacted with alkali and carries out salinization.In addition, the application the invention also discloses above-mentioned ionomer as nucleating agent in being modified to PET.The ionomer that the present invention obtains is preferable to the nucleating effect of PET, and preparation process is simple, environmentally protective.
Description
Technical field
The present invention relates to polymeric material fields, and in particular, to microspheroidal ionomer and its system with cross-linked structure
Preparation Method and application.
Background technique
Ionomer abbreviation ionomer or from aggressiveness is the polymerization that a small amount of ionic group is had on a kind of macromolecular chain
Object material, wherein the molar content of ionic group is no more than 15%.Ionomer is inorganic ions and organic molecule perfect combination
Entity has the unexistent Specific Interactions of general polymerization object due to the introducing of ionic group between ionomer interior molecules,
Such as ion and ionic interaction；Ion pair and ion Thermodynamic parameters；Ion and dipolar interaction；Interaction of hydrogen bond
Deng.These special interactions are so that ionomer has many unique performances, and in the side such as polymer modification, functional material
There is important use in face.
In addition, the preparation of polymer microballoon at present and the research of application aspect are a heat of functional polymer material field
Point, nanoscale to micron-sized polymer microballoon has large specific surface area, strong adsorption, cohesion big and energy is reacted on surface
The strong special nature of power, can be widely applied to many high-technology fields.
102924641 A of CN discloses a kind of polyethylene terephthalate (PET) nucleating agent and preparation method thereof,
The random copolymer or alternate copolymer that the nucleating agent is styrene and maleic anhydride are through hydrolysis, salinization and purification benzene obtained
Ethylene/maleic acid ionomer.Preparation method includes: that maleic anhydride monomer, styrene monomer, initiator and solvent are uniformly mixed,
In nitrogen atmosphere, after 60-80 DEG C of heating is reacted 1-1.5 hours, reaction product is precipitated in a solvent, is purified, vacuum drying,
Copolymer is obtained, then copolymer is dissolved in Isosorbide-5-Nitrae-dioxane, alkali alcosol is added dropwise, by the ionomer of generation from precipitating reagent
It is precipitated, is filtered by vacuum, purification obtains styrene/maleic acid ionomer.PET crystallization temperature can be improved in the ionomer, accelerates crystallization
Rate.
103145903 A of CN discloses a kind of polyethylene terephthalate (PET) nucleating agent and preparation method thereof,
Nucleating agent is that poly- (styrene-alt- maleic anhydride) di-block copolymer of polystyrene-b- is made through hydrolysis, salinization and purification
Polystyrene-b- poly- (styrene-alt- maleic anhydride) two Block copolymer ionomers.The nucleating agent can form micro- in PET melt
It mutually separates, to provide nucleus for PET crystallization.
Li Dongying, Pei Guangling etc. are in " influence of the crosslinking agent adding manner to polystyrene microsphere pattern and dispersion performance "
It is micro- that about 1 micron of partial size of monodisperse cross-linked polystyrene is prepared in (" chemical research ", 2014,25 (3): 293-297) text
Ball has studied crosslinker concentration, and influence of the time to microballoon pattern and dispersion performance is added.
But polymer made from the above method is still improved space to the nucleating effect of PET.
Summary of the invention
The object of the present invention is to overcome the deficiencies of the prior, provides a kind of microspheroidal with cross-linked structure
Method of ionomer and its preparation method and application, ionomer of the invention have good nucleating effect to PET.
It was found by the inventors of the present invention that drawing during maleic anhydride and styrene (or α-methylstyrene) monomer polymerization
The ionomer excellent to the nucleating effect of PET can be obtained by entering crosslinking agent, therefore, to achieve the goals above, a side of the invention
Face provides a kind of method for preparing the microspheroidal ionomer with cross-linked structure, this method comprises:
(1) in organic solvent, in the presence of first part's initiator, maleic anhydride and first part monomer M are connect
Touching is reacted, and being re-introduced into the solution containing crosslinking agent, the reaction was continued, wherein the solution containing crosslinking agent contains crosslinking agent, appoints
The second part monomer M of choosing and optional second part initiator, the structure of monomer M are represented by a formula X:
In Formula X, R is H or methyl；
(2) in presence of water, step (1) products therefrom is contacted with alkali and carries out salinization.
Second aspect of the present invention provides ionomer made from the method as described in first aspect.
Third aspect present invention provides above-mentioned ionomer as nucleating agent and carries out to polyethylene terephthalate
Application in modification.
The ionomer (or ionomer microballoon) that the present invention obtains has crosslinking and micro-sphere structure, to the nucleating effect of PET compared with
It is good, and preparation process is simple, it is micro- to can be obtained ionomer through simple lock out operation (without using precipitating reagent) after reaction
Ball, it is environmentally protective.
Moreover, in a preferred embodiment of the invention, the ionomer is made by one kettle way technique, it is outstanding after polymerization
Supernatant liquid is directly reacted with alkali without being separated and being dried, to further simplify process flow, reduce energy consumption.
Detailed description of the invention
Fig. 1 is the infrared spectrogram of the ionomer synthesized according to one embodiment of the present invention (embodiment 1)；
Fig. 2 is the stereoscan photograph of the ionomer synthesized according to one embodiment of the present invention (embodiment 1)；
Fig. 3 is the ionomer that synthesize according to one embodiment of the present invention (embodiment 1), and through solvent, treated that scanning is electric
Mirror photo；
Fig. 4 is the stereoscan photograph for the ionomer that comparative example 1 synthesizes；
Fig. 5 is the ionomer that synthesizes of comparative example 1 through solvent treated stereoscan photograph.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
There is the method for microspheroidal ionomer of cross-linked structure to include: for preparation provided by the invention
(1) in organic solvent, in the presence of first part's initiator, maleic anhydride and first part monomer M are connect
Touching is reacted, and being re-introduced into the solution containing crosslinking agent, the reaction was continued, wherein the solution containing crosslinking agent contains crosslinking agent, appoints
The second part monomer M of choosing and optional second part initiator, the structure of monomer M are represented by a formula X:
In Formula X, R is H or methyl；
(2) in presence of water, step (1) products therefrom is contacted with alkali and carries out salinization (or hydrolysis).
The amount ratio of maleic anhydride and monomer M can be conventional selection, but in a preferred embodiment of the invention, phase
For the maleic anhydride of 100mol, total dosage of first part monomer M and second part monomer M are 50-150mol, more preferably
75-100mol.It will be appreciated to those of skill in the art that monomer M is α-methylstyrene or styrene.
In step (1) of the invention, monomer M can be fed intake (i.e. the amount of second part monomer M can be zero) with a step, can also
To be divided into two parts feed intake (i.e. first part's monomer M and second part monomer M).Preferred embodiment according to the present invention, the
Molar ratio between two partial monosomy M and first part monomer M be 0-100:100 (such as 0,1:100,5:100,15:100,25:
100, between 30:100,45:100,50:100,60:100,70:100,80:100,90:100,100:100 or above-mentioned numerical value
Arbitrary value).
In the present invention, the dosage of organic solvent can be conventional selection, as long as the reaction for step (1) provides medium i.e.
It can, it is preferable that relative to the maleic anhydride of 100mol, the dosage of organic solvent is 50-150L.
In step (1) of the invention, the solvent that the organic solvent can be common for various solution polymerizations, for example,
The organic solvent includes organic acid alkylester did, also can be the mixed of organic acid alkylester did or organic acid alkylester did and alkane
Close the mixture of object or organic acid alkylester did and aromatic hydrocarbon.Wherein, the organic acid alkylester did includes but is not limited to: formic acid first
Ester, Ethyl formate, propyl formate, butyl formate, iso-butyl formate, amyl formate, methyl acetate, ethyl acetate, propyl acetate,
Butyl acetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, isoamyl acetate, benzyl acetate, methyl propionate, propionic acid second
Ester, butyl propionate, methyl butyrate, ethyl butyrate, butyl butyrate, isobutyl isobutyrate (IBIB), isoamyl butyrate, iso-amyl iso-valeriate, benzene
Methyl formate, ethyl benzoate, propyl benzoate, butyl benzoate, isoamyl benzoate, methyl phenylacetate and ethyl phenylacetate
At least one of.The alkane includes but is not limited to: n-hexane and/or normal heptane.The aromatic hydrocarbon includes but is not limited to:
At least one of benzene, toluene and dimethylbenzene.
In the present invention, the dosage of the initiator is not required particularly, it is preferable that the maleic acid relative to 100mol
Total dosage of acid anhydride, first part's initiator and second part initiator is 0.05-10mol, more preferably 0.8-1.5mol.
In step (1) of the invention, initiator can feed intake (i.e. the amount of second part initiator can be zero) with a step,
Feed intake (i.e. first part's initiator and second part initiator) can be divided into two parts.Preferred embodiment party according to the present invention
Formula, molar ratio between second part initiator and first part's initiator be 0-100:100 (such as 0,1:100,5:100,15:
100,25:100,30:100,45:100,50:100,60:100,70:100,80:100,90:100,100:100 or above-mentioned numerical value
Between arbitrary value).
In step (1) of the invention, the initiator can be commonly used in for this field causes maleic anhydride and α-first
The reagent of the polymerization reaction of base styrene (or styrene) can be heat decomposition type initiator.Under preferable case, the initiator
Selected from dibenzoyl peroxide, cumyl peroxide, di-tert-butyl peroxide, dilauroyl peroxide, perbenzoic acid
The tert-butyl ester, diisopropyl peroxydicarbonate, dicetyl peroxydicarbonate dicyclohexyl ester, azodiisobutyronitrile and azo two different heptan
At least one of nitrile.
In the present invention, the dosage of crosslinking agent is not particularly limited, it is preferable that relative to the maleic anhydride of 100mol,
The dosage of crosslinking agent is 1-40mol, more preferably 10-20mol.
In the present invention, crosslinking agent can for more than various two common degrees of functionality be able to carry out free radical polymerization containing ethylene
Base monomer.Under preferable case, the crosslinking agent is divinylbenzene and/or the propylene containing at least two esters of acrylic acid groups
Esters of gallic acid crosslinking agent, the structural formula of the esters of acrylic acid group are as follows:-O-C (O)-C (R ')=CH2, R ' is H or C1-C4Alkane
Base (such as methyl).
It is highly preferred that the crosslinking agent is selected from divinylbenzene, bis- (methyl) acrylate (such as dimethyl propylenes of propandiols
Olefin(e) acid -1,3- propylene glycol ester, dimethacrylate -1,2- propylene glycol ester, diacrylate -1,3- propylene glycol ester, diacrylate -1,
2- propylene glycol ester), glycols bis- (methyl) acrylate (ethylene glycol dimethacrylate, ethylene glycol diacrylate, two
Ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, two propylene of triethylene glycol
Acid esters, tetraethylene glycol dimethylacrylate, tetraethylene glycol diacrylate), trimethylolpropane trimethacrylate, three hydroxyl first
Base propane trimethyl acrylic ester, polyethyleneglycol diacrylate, polyethylene glycol double methyl methacrylate, phthalic acid diethyl
Omega-diol diacrylate, pentaerythritol tetraacrylate, five acrylate of dipentaerythrityl ether, six acrylic acid of dipentaerythrityl ether
At least one of ester and the multi-functional degree acrylate of ethoxylation.
In step (1), maleic anhydride contacted with monomer M first reacted namely maleic anhydride and monomer M unreacted it is complete
Entirely, only part has carried out polymerization reaction in the presence of initiator.Maleic anhydride contacts the condition reacted with monomer M can be with
For conventional condition, as long as polymerization reaction only partially occurs for control maleic anhydride and monomer M, it is preferable that maleic anhydride with
The condition that monomer M contact is reacted includes: inert atmosphere, and temperature is 50-90 DEG C (further preferably 60-70 DEG C), the time
For 0.5-4h (further preferably 0.5-2h).
In step (1), after maleic anhydride contacts with monomer M and to carry out part reaction, introduce the solution containing crosslinking agent after
Continuous reaction, to be particularly beneficial in forming shell-crosslinked structure.The condition that the reaction was continued can be conventional condition, as long as making
Each substrate participates in reaction as far as possible, it is preferable that the condition that the reaction was continued includes: that temperature is 50-90 DEG C, time 2-15h.
Preferred embodiment according to the present invention introduces the mode that the reaction was continued of the solution containing crosslinking agent are as follows: in 50-90 DEG C (into one
Preferably 60-70 DEG C of step) under, the solution containing crosslinking agent is added dropwise in step (1) products therefrom in 1-3h, is further continued for keeping the temperature
React 1-4h.
In the present invention, the type and content of solvent in the solution containing crosslinking agent are not required particularly, as long as making it
In solute sufficiently dissolve, in general, the solvent type in the solution containing crosslinking agent can with the organic solvent have phase
Same selection (namely as previously mentioned including organic acid alkylester did), and the content of crosslinking agent can be in the solution containing crosslinking agent
0.5-3mol/L。
In step (2) of the invention, the use of alkali accounts for the mole of metal cation in the ionomer in ionomer
Maleic anhydride provide structural unit integral molar quantity percentage in a certain range, preferably within the above range.The alkali
Dosage can be conventional selection, it is preferable that relative to the maleic anhydride of 100mol, the dosage of the alkali be 10-200mol (such as
Arbitrary value between 10mol, 50mol, 100mol, 150mol, 190mol, 200mol or above-mentioned numerical value).The alkali is preferably with water
The form of solution uses, and the concentration of the aqueous solution of alkali is preferably 1-30 weight %.
In step (2) of the invention, the alkali (can be capable of providing metal sun for alkaline matter commonly used in the art
The alkaline matter of ion (as previously described)), as long as the part carboxyl hydrogen in the polymer that the step (1) after hydrolysis can be made to obtain
Replaced by metal.Preferably, the alkali is selected from the hydroxide of metal and/or the acetate of metal.The metal can be with
For monovalent metal, or divalent metal, as IA race, Group IIA and/or Group IIB metal (especially lithium, sodium, potassium, calcium, barium,
Zinc and/or magnesium).It is highly preferred that the alkali is selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, hydrogen
At least one of zinc oxide, magnesium hydroxide, lithium acetate, sodium acetate, potassium acetate, calcium acetate, barium acetate and zinc acetate.
In step (2) of the invention, the salinization can carry out under normal conditions, for example, the condition packet of the salinization
Include: temperature is 20-100 DEG C (preferably 30-100 DEG C), and the time is 0.5-8h (preferably 0.5-6h).
In step (2) of the invention, can also step (1) products therefrom (suspension) is post-treated (separation, washing and
It is dry) it is reacted again with alkali later.The washing can using conventional cleaning solvent, for example, n-hexane, isohexane, hexamethylene,
In normal heptane, normal octane, isooctane, methanol, ethyl alcohol, normal propyl alcohol, isopropanol, ether, isopropyl ether and methyl tertiary butyl ether(MTBE) extremely
Few one kind.What is obtained after salinization in this way is the dispersion containing ionomer, which is through further separating treatment
Ionomer products can be obtained, for example, carrying out separating treatment in the following way: centrifuge separation, washing, organic solvent washing (can
With use foregoing cleaning solvent namely n-hexane, isohexane, hexamethylene, normal heptane, normal octane, isooctane, methanol,
At least one of ethyl alcohol, normal propyl alcohol, isopropanol, ether, isopropyl ether and methyl tertiary butyl ether(MTBE)), centrifuge separation is dry (as very
Sky is dry).
The present inventor has found under study for action, without directly obtain step (1) except organic solvent step
Suspension, which reacts progress salinization with alkali, also can effectively be made ionomer of the invention.Therefore, preferred implementation side according to the present invention
Formula in step of the invention (2), step (1) products therefrom can directly be reacted with alkali (one kettle way), be obtained after such salinization
Be the mixed system containing ionomer, which can be obtained ionomer products through further separating treatment, for example,
Carry out separating treatment: stratification in the following way, organic phase is for being recycled, and heavy phase is centrifuged, washing-centrifugation
Separation, dry (as being dried in vacuo) and ionomer.This preferred method uses one kettle way technique, and product post-processing only needs one
Secondary Liquid liquid Separation, separation of solid and liquid, washing and drying, the single batch that effectively shortens is time-consuming, simplifies process flow, reduces unit and set
It is standby, effectively reduce energy consumption；The technique only needs a kind of organic solvent as reaction medium, and solvent only needs layering, drying process
It can be recycled, and be not necessarily to special division box, layering can be realized in the reactor, solvent is recycled without distillation
Purifying, it is energy-saving, it can effectively reduce the pollution using organic solvent to environment.
The present invention also provides ionomers made from the above method.Ionomer produced by the present invention has cross-linked structure and is in
Microspheroidal.Leachable≤10 weight % (such as 1 weight %, 2 weights of the ionomer of the invention 30min in 5 times of weight, 50 DEG C of acetone
Measure %, 2.5 weight %, 4 weight %, 5.5 weight %, 6.5 weight %, 7.5 weight %, 8.5 weight %, 10 weight % or above-mentioned
Arbitrary value between numerical value), solvent resistance is strong.In the present invention, according to a kind of preferred embodiment, metal in the ionomer
The mole of cation account for the integral molar quantity for the structural unit A that maleic anhydride in ionomer provides 10-100% (such as 10%,
20%, any between 30%, 40%, 50%, 60%, 70%, 80%, 85%, 90%, 95%, 100% or above-mentioned numerical value
Value).The degree of cross linking of the ionomer preferably >=65% (such as 65%, 70%, 75%, 80%, 85%, 90% or above-mentioned numerical value it
Between arbitrary value).The average grain diameter of the ionomer be 150-2000nm (such as 150nm, 250nm, 350nm, 450nm, 550nm,
650nm、750nm、850nm、950nm、1050nm、1150nm、1250nm、1350nm、1450nm、1550nm、1650nm、
Arbitrary value between 1750nm, 1850nm, 2000nm or above-mentioned numerical value).The ionomer has shell-crosslinked structure, therefore has
There are more preferably solvent resistance and thermal stability.In the present invention, metal cation can be various common metal ions, for example,
Li+、Na+、K+、Ca2+、Mg2+、Ba2+Or Zn2+, molar content pass through X-ray fluorescence spectra analysis obtain.The degree of cross linking indicates
Gel content is measured by solvent extraction process.The average grain diameter is characterized with number average bead diameter, is surveyed by scanning electron microscope
?.
In addition, the application the present invention also provides above-mentioned ionomer as nucleating agent in being modified to PET.In reality
In use, ionomer and PET of the invention can be carried out melt blending.Relative to 100 grams of PET, the use of the ionomer
Amount can be 0.5-5g.The temperature of the melt blending can be 250-300 DEG C.The time of the melt blending can be 5-
8min.Product through melt blending carries out extruding pelletization again can be obtained modified PET product.
The present invention will be described in detail by way of examples below.It is vacuum drying in following embodiment and comparative example
Condition are as follows: 100 DEG C, vacuum degree is -0.095MPa, time 8h.
Embodiment 1
The present embodiment be used to illustrate the microspheroidal ionomer (or ionomer microballoon) with cross-linked structure of the invention and
Preparation method.
(1) maleic anhydride 1000g, α-methylstyrene 1180g and azodiisobutyronitrile 20g are dissolved in 8L isoamyl acetate
In, under nitrogen atmosphere, reacted 1 hour at 70 DEG C；
(2) it is solution two that divinylbenzene 260g, which is dissolved in 2L isoamyl acetate, and solution two is added drop-wise to
It in the reaction system of step (1), is added dropwise 2 hours, after completion of dropwise addition, reaction system continues insulation reaction 3 hours；
(3) sodium hydrate aqueous solution 3500g (14wt%) is added after reacting, is reacted 3 hours at 80 DEG C.System after reaction
Stratification, heavy phase are centrifugated 20 minutes under the conditions of 5000rad/min through centrifuge, and solid adds 4L water agitator treating, warp
Centrifuge is centrifugated 20 minutes under the conditions of 5000rad/min, and solid adds 4L water agitator treating, through centrifuge in 5000rad/
It is centrifugated 20 minutes under the conditions of min, solid vacuum drying obtains shell-crosslinked α-methylstyrene/maleic acid sodium salt from poly-
Object microballoon (is denoted as C1), and Fig. 2 shows its scanning electron microscope (SEM) photographs, it can be seen that C1 is the microballoon of dispersion.
(4) system after step (2) reaction is centrifugated 30 minutes under the conditions of 5000rad/min through centrifuge, is obtained
To crosslinking α-methylstyrene/maleic anhydride polymer microballoon, methanol washing purifying, vacuum drying.Add sodium hydroxide water
Solution 3500g (10wt%) reacts 3 hours at 80 DEG C.System after reaction is centrifuged under the conditions of 5000rad/min through centrifuge
Separation 30 minutes, solid adds 400mL water agitator treating, is centrifugated 30 minutes under the conditions of 5000rad/min through centrifuge, Gu
Body adds 500mL methanol agitator treating, is centrifugated 30 minutes under the conditions of 5000rad/min through centrifuge, solid vacuum drying,
Obtain shell-crosslinked α-methylstyrene/maleic acid sodium salt ionomer microballoon (being denoted as C1-1).
(5) the shell-crosslinked α-methylstyrene of 10.00g/maleic acid sodium salt ionomer microballoon C1 is weighed, 50g third is added to
In ketone, 30min is stirred at 50 DEG C.System is centrifugated 30 minutes under the conditions of 5000rad/min through centrifuge, vacuum drying
After weigh, polymer 9.38g, leachable 0.62g.Fig. 3 shows solvent treated ionomer microballoon scanning electron microscope (SEM) photograph.
Compare Fig. 2 and Fig. 3 can be seen that by after solvent is handled ionomer microballoon pattern change it is smaller.
Embodiment 2
The present embodiment is used to illustrate ionomer microballoon and preparation method thereof of the invention.
(1) maleic anhydride 1000g, α-methylstyrene 900g and azodiisobutyronitrile 20g are dissolved in 7L isoamyl acetate
In, under nitrogen atmosphere, reacted 2 hours at 70 DEG C；
(2) it is solution two that α-methylstyrene 200g and divinylbenzene 260g, which is dissolved in 3L isoamyl acetate, by solution two
It is added drop-wise in the reaction system of step (1), is added dropwise 3 hours, after completion of dropwise addition, reaction system continues insulation reaction 3 hours；
(3) sodium acetate aqueous solution 4000g (20wt%) is added after reacting, is reacted 4 hours at 100 DEG C.System after reaction
Stratification, heavy phase are centrifugated 20 minutes under the conditions of 5000rad/min through centrifuge, and solid adds 4L water agitator treating, warp
Centrifuge is centrifugated 20 minutes under the conditions of 5000rad/min, and solid adds 4L water agitator treating, through centrifuge in 5000rad/
It is centrifugated 20 minutes under the conditions of min, solid vacuum drying obtains shell-crosslinked α-methylstyrene/maleic acid sodium salt from poly-
Object microballoon (is denoted as C2)；
(4) the shell-crosslinked α-methylstyrene of 10.00g/maleic acid sodium salt ionomer microballoon is weighed, 50g acetone is added to
In, 30min is stirred at 50 DEG C.System is centrifugated 30 minutes under the conditions of 5000rad/min through centrifuge, after vacuum drying
Weighing, polymer 9.44g, leachable 0.56g.It is similar with C1, solvent before and after the processing microballoon pattern change it is smaller.
Embodiment 3
The present embodiment is used to illustrate ionomer microballoon and preparation method thereof of the invention.
(1) maleic anhydride 1000g, α-methylstyrene 1020g and azodiisobutyronitrile 15g are dissolved in 8L acetic acid isoamyl
Ester under nitrogen atmosphere, reacts 0.5 hour at 70 DEG C；
(2) it is solution two that divinylbenzene 260g and azodiisobutyronitrile 5g, which is dissolved in 2L isoamyl acetate, and solution two is dripped
It is added in the reaction system of step (1), is added dropwise 2 hours, after completion of dropwise addition, reaction system continues insulation reaction 4 hours；
(3) zinc acetate aqueous solution 9000g (20wt%) is added after reacting, is reacted 7 hours at 100 DEG C.System after reaction
Stratification, heavy phase are centrifugated 20 minutes under the conditions of 5000rad/min through centrifuge, and solid adds 4L water agitator treating, warp
Centrifuge is centrifugated 20 minutes under the conditions of 5000rad/min, and solid adds 4L water agitator treating, through centrifuge in 5000rad/
It is centrifugated 20 minutes under the conditions of min, solid vacuum drying obtains shell-crosslinked α-methylstyrene/maleic acid zinc salt from poly-
Object microballoon (is denoted as C3)；
(4) the shell-crosslinked α-methylstyrene of 10.00g/maleic acid zinc salt ionomer microballoon is weighed, 50g acetone is added to
In, 30min is stirred at 50 DEG C.System is centrifugated 30 minutes under the conditions of 5000rad/min through centrifuge, after vacuum drying
Weighing, polymer 9.74g, leachable 0.26g.It is similar with C1, solvent before and after the processing microballoon pattern change it is smaller.
Embodiment 4
The present embodiment is used to illustrate ionomer microballoon and preparation method thereof of the invention.
(1) maleic anhydride 1000g, α-methylstyrene 910g and azodiisobutyronitrile 20g are dissolved in 7L isoamyl acetate
In, under nitrogen atmosphere, reacted 1 hour at 70 DEG C；
(2) it is solution two that α-methylstyrene 200g and divinylbenzene 260g, which is dissolved in 3L isoamyl acetate, by solution two
It is added drop-wise in the reaction system of step (1), is added dropwise 3 hours, after completion of dropwise addition, reaction system continues insulation reaction 3 hours；
(3) lithium hydroxide aqueous solution 2000g (10wt%) is added after reacting, is reacted 5 hours at 100 DEG C.Body after reaction
It is stratification, heavy phase is centrifugated 20 minutes under the conditions of 5000rad/min through centrifuge, and solid adds 4L water agitator treating,
It is centrifugated 20 minutes under the conditions of 5000rad/min through centrifuge, solid adds 4L water agitator treating, exists through centrifuge
It is centrifugated 20 minutes under the conditions of 5000rad/min, solid vacuum drying obtains shell-crosslinked α-methylstyrene/maleic acid
Lithium salts ionomer microballoon (being denoted as C4)；
(4) the shell-crosslinked α-methylstyrene of 10.00g/maleic acid lithium salts ionomer microballoon is weighed, 50g acetone is added to
In, 30min is stirred at 50 DEG C.System is centrifugated 30 minutes under the conditions of 5000rad/min through centrifuge, after vacuum drying
Weighing, polymer 9.29g, leachable 0.71g.It is similar with C1, solvent before and after the processing microballoon pattern change it is smaller.
Embodiment 5
The present embodiment is used to illustrate ionomer microballoon and preparation method thereof of the invention.
(1) maleic anhydride 100g, α-methylstyrene 58g, azodiisobutyronitrile 2g are dissolved in 700mL isoamyl acetate
In, under nitrogen atmosphere, reacted 0.5 hour at 80 DEG C；
(2) it is solution two that divinylbenzene 38g, which is dissolved in 100mL isoamyl acetate, and solution two is added drop-wise to the anti-of step (1)
It answers in system, is added dropwise 2 hours, after completion of dropwise addition, reaction system continues insulation reaction 3 hours；System after reaction is through centrifuge
It is centrifugated 30 minutes under the conditions of 5000rad/min, obtains crosslinking α-methylstyrene/maleic anhydride polymer microballoon, first
Alcohol washing purifying, vacuum drying.
(3) sodium hydroxide 14g is dissolved in 350mL water, will be crosslinked α-methylstyrene/maleic anhydride polymer microballoon 50g
It is added in sodium hydrate aqueous solution (relative to every mole of maleic anhydride, the dosage of alkali is 1.8mol), reacts 3 at 100 DEG C
Hour.System after reaction is centrifugated 30 minutes under the conditions of 5000rad/min through centrifuge, and solid adds 400mL water to stir
Washing, is centrifugated 30 minutes under the conditions of 5000rad/min, solid adds 500mL methanol agitator treating, through being centrifuged through centrifuge
Machine is centrifugated 30 minutes under the conditions of 5000rad/min, and solid vacuum drying obtains crosslinking α-methylstyrene/maleic acid
Sodium salt ionomer microballoon (being denoted as C5)；
(4) the shell-crosslinked α-methylstyrene of 10.00g/maleic acid sodium salt ionomer microballoon is weighed, 50g acetone is added to
In, 30min is stirred at 50 DEG C.System is centrifugated 30 minutes under the conditions of 5000rad/min through centrifuge, after vacuum drying
Weighing, polymer 9.35g, leachable 0.65g.It is similar with C1, solvent before and after the processing microballoon pattern change it is smaller.
Embodiment 6
Ionomer microballoon is prepared according to the method for embodiment 1, unlike, the dosage of divinylbenzene is 100g, is obtained
Ionomer microballoon C6.
The shell-crosslinked α-methylstyrene of 10.00g/maleic acid sodium salt ionomer microballoon is weighed, is added in 50g acetone,
30min is stirred at 50 DEG C.System is centrifugated 30 minutes under the conditions of 5000rad/min through centrifuge, is claimed after vacuum drying
Weight, polymer 9g, leachable 1g.
Comparative example 1
(1) maleic anhydride 1000g, α-methylstyrene 1180g, divinylbenzene 260g, azodiisobutyronitrile 20g is molten
In 10L isoamyl acetate, under nitrogen atmosphere, reacted 5 hours at 70 DEG C；
(2) sodium hydrate aqueous solution 3500g (14wt%) is added after reacting, is reacted 3 hours at 80 DEG C.System after reaction
Stratification, heavy phase are centrifugated 20 minutes under the conditions of 5000rad/min through centrifuge, and solid adds 4L water agitator treating, warp
Centrifuge is centrifugated 20 minutes under the conditions of 5000rad/min, and solid adds 4L water agitator treating, through centrifuge in 5000rad/
It is centrifugated 20 minutes under the conditions of min, it is micro- to obtain crosslinking α-methylstyrene/maleic acid sodium salt ionomer for solid vacuum drying
Ball (is denoted as C-D1), and Fig. 4 shows ionomer microballoon scanning electron microscope (SEM) photograph；
10.00g crosslinking α-methylstyrene/maleic acid sodium salt ionomer microballoon is weighed, is added in 50g acetone, 50
30min is stirred at DEG C.System is centrifugated 30 minutes under the conditions of 5000rad/min through centrifuge, is weighed after vacuum drying, is gathered
Conjunction object is 8.51g, leachable 1.49g.Fig. 5 shows solvent treated ionomer microballoon, it can be seen that comparative example 1
Polymer does not have shell-crosslinked structure, and before solvent processing, microballoon pattern changes larger.
Comparative example 2
(1) α-methylstyrene for weighing 98g maleic anhydride and 118g is placed in three-necked flask, and two isobutyl of 2g azo is added
Nitrile is initiator, and q. s. toluene is added and does reaction dissolvent, under nitrogen atmosphere, reacts 5 hours at 70 DEG C.By polymer after reaction
It is filtered, filter cake is washed 3 times with toluene, and vacuum drying obtains α-methylstyrene/maleic anhydride polymer；
(2) α-methylstyrene/maleic anhydride polymer of 20.2g is dissolved in Isosorbide-5-Nitrae-dioxane of 200mL, is added
The saturated aqueous solution of 4g sodium hydroxide reacts 3 hours at room temperature.After reaction, ionomer solid is obtained by filtration.Solid vacuum is dry
It is dry, obtain α-methylstyrene/maleic acid sodium salt ionomer (being denoted as polymer C-D2).
α-methylstyrene/maleic acid sodium salt ionomer the microballoon for weighing 10.00g, is added in 50g acetone, at 50 DEG C
Lower stirring 30min.System is centrifugated 30 minutes under the conditions of 5000rad/min through centrifuge, is weighed after vacuum drying, polymerization
Object is 1.04g, leachable 8.96g.
Comparative example 3
Ionomer microballoon is prepared according to the method for embodiment 1, unlike, the crosslinking agent of 260g is divided into two parts and introduces instead
Answer system, wherein 130g crosslinking agent is dissolved in isoamyl acetate with maleic anhydride in step (1) and being reacted, in addition
130g crosslinking agent introduces reaction system in step (2), obtains ionomer microballoon C-D3.
α-methylstyrene/maleic acid sodium salt ionomer the microballoon for weighing 10.00g, is added in 50g acetone, at 50 DEG C
Lower stirring 30min.System is centrifugated 30 minutes under the conditions of 5000rad/min through centrifuge, is weighed after vacuum drying, polymerization
Object is 8.92g, leachable 1.08g.
Test case 1
(1) infrared spectrum analysis is carried out to the ionomer microballoon that embodiment 1 obtains, as a result as shown in Figure 1, from infrared spectroscopy
Analysis result can be seen that ionomer successfully synthesizes, the results of IR of embodiment 2-6 is similar to Example 1, at
Function has obtained crosslinked ionomers.
(2) the ionomer microballoon prepared in above-described embodiment is subjected to X-ray fluorescence spectra analysis, to measure ionomer
In metal cation content.
(3) average grain diameter and the degree of cross linking (the partial size test side of the polymer prepared in above-described embodiment and comparative example are measured
Method: 500 microballoons are chosen in electromicroscopic photograph, its diameter is measured, the average grain diameter of microballoon is calculated with mathematic(al) mean method；Crosslinking
Degree measuring method: 2-3 grams of polymer microballoon (w1) is weighed, is wrapped using middling speed qualitative filter paper, is put into Soxhlet extractor, use four
Hydrogen furans extracts 24 hours, and the degree of cross linking is calculated by w2/w1 in the dry weighing w2 of polymer), as a result as shown in table 1 below.
Table 1
(4) the ionomer microballoon prepared in above-described embodiment and comparative example is uniformly mixed with PET respectively, ionomer microballoon
Additive amount be PET mass 1 weight %, then melt blending 8 minutes, extruding pelletization at 280 DEG C obtain modified poly-
Ethylene glycol terephthalate.Modified PET carries out differential scanning calorimetry (DSC) test, and using unmodified PET as pair
According to the results are shown in Table 2.
Table 2
| Project | Fusion-crystallization peak/DEG C | Peak value/DEG C | Half-peak breadth/DEG C | ΔH/J·g-1 |
| PET | — | 151.7 | 23.3 | -11.3 |
| C1 modified PET | 123.3 | 208.8 | 6.2 | -35.8 |
| C1-1 modified PET | 122.5 | 207.9 | 6.5 | -36.0 |
| C2 modified PET | 124.5 | 205.8 | 6.8 | -35.2 |
| C3 modified PET | 122.9 | 206.1 | 7.2 | -35.0 |
| C4 modified PET | 125.4 | 205.1 | 7.1 | -35.8 |
| C5 modified PET | 127.0 | 202.8 | 7.2 | -33.9 |
| C6 modified PET | 132.1 | 197.3 | 9.0 | -32.8 |
| C-D1 modified PET | 129.5 | 202.2 | 6.4 | -36.8 |
| C-D2 modified PET | 134.7 | 195.2 | 10.2 | -35.0 |
| C-D3 modified PET | 126.5 | 203.9 | 7.9 | -35.7 |
It can be seen that using ionomer made from the method for the present invention as the result of table 2 with more obvious than comparative example more preferable
The nucleating effect to PET, be remarkably improved the crystallization temperature of PET, accelerate crystalline rate；Moreover, being opened compared in reaction one
Begin the comparative example 1 for just adding crosslinking agent, and the micro-sphere structure which has shell highly cross-linked is shown preferably resistance to molten
Agent and thermal stability, in the modified ionomer of salinization, microsphere surface is more smooth, so the ionomer that the present invention obtains exists
There is preferably dispersibility, solvent resistance and thermal stability in PET modification application.The ionomer nucleating effect of embodiment 1-5 is excellent
In the nucleating agent of the ionomer of comparative example；In addition, comparing non-crosslinked α-methylstyrene/sodium maleate without micro-sphere structure
Salt ionomer has more preferably nucleating effect to PET.
In addition, comparing embodiment 1 is with embodiment 6 as can be seen that the dosage of control crosslinking agent can obtain in preferred scope
Obtain more preferably nucleating effect.
Test case 2
In the test case, PET is purchased from Sinopec Yizheng Fiber Optical plant, intrinsic viscosity 0.7dl/g；Nitrogen phosphorous halogen-free flame retardants
(HT202A) it is purchased from Jinan Taixing Fine Chemicals Co., ltd；Lubricant (PET100) is purchased from Britain's standing grain major company；Glass fibre
(or glass or GF) is purchased from Zhejiang Jushi Group Co., Ltd.；Processing aid antioxidant is purchased from Ciba Specialty Chemicals.Specific steps
It is as follows:
Weighing 100 parts by weight PET, 1.5 parts by weight ionomer microballoons, 0.2 parts by weight processing aid, (weight ratio is 1:1's
Antioxidant 1010 and irgasfos 168), 8 parts by weight of flame retardant, 0.04 parts by weight lubricant be put into high-speed mixer stir it is equal
It is even, using WP ZSK25 twin-screw, squeezed out at a temperature of temperature of each section is 230-245-255-260-260-260 DEG C；Glass
It is added in twin-screw feed opening；Nitrogen phosphorous halogen-free flame retardants (HT202A) is added by side feeding, squeezes out cooling granulation, is done
Dry (100 DEG C, 8h) are injected into standard sample of photo (mold with 125 injector of extra large day afterwards at a temperature of 230-240-255-260-260 DEG C
Temperature 60 C), it is tested for the property:
It is obtained using 300 grams of injectors (manufacture of Ningbo Hai Tian company) injection having a size of 250 millimeters of (length) × 25 millimeter
The standard batten of (width) × 10 millimeter (thickness) measures the standard batten with GB/T1040-1992 plastic tensile method for testing performance
Tensile strength and elongation at break；
It is obtained using 300 grams of injectors (manufacture of Ningbo Hai Tian company) injection having a size of 80 millimeters of (length) × 10 millimeter (width)
× 4 millimeters (thickness) of standard batten measures the bending of the standard batten with GB/T9341-2008 Plastics-Oetermination of flexural properties method
Intensity and bending modulus；
It is obtained using 300 grams of injectors (manufacture of Ningbo Hai Tian company) injection having a size of 80 millimeters of (length) × 10 millimeter (width)
× 4 millimeters (thickness), the standard batten that notch is 2 millimeters is surveyed with the measuring method of GB/T1043-93 plastics cantilever beam impact strength
Calibrate the simply supported beam notch impact strength of quasi- batten；
Deformation: two injection molding sample square pieces (60mm × 60mm × 2mm) are taken, one of them is placed in 120 DEG C
3 hours in baking oven, a room temperature observes the deformation of print.
The results show that the use of ionomer of the present invention can make the tensile strength of the plastic products obtained in 120-145MPa
In range, elongation at break is about 2%, bending strength within the scope of 140-190MPa, bending modulus within the scope of 6-10GPa,
Simply supported beam notch impact strength is in 5.5-10kJ/m2In range, it is placed in 3 hours in 120 DEG C of baking ovens and does not observe apparent deformation.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (10)
1. a kind of method for preparing the microspheroidal ionomer with cross-linked structure, which is characterized in that this method comprises:
(1) in organic solvent, in the presence of first part's initiator, by maleic anhydride and first part monomer M contact into
Row reaction, being re-introduced into the solution containing crosslinking agent, the reaction was continued, wherein the solution containing crosslinking agent contains crosslinking agent, optional
Second part monomer M and optional second part initiator, the structure of monomer M are represented by a formula X:
In Formula X, R is H or methyl；
(2) in presence of water, step (1) products therefrom is contacted with alkali and carries out salinization.
2. according to the method described in claim 1, wherein, relative to the maleic anhydride of 100mol, first part monomer M and second
Total dosage of partial monosomy M is 50-150mol, preferably 75-100mol；The dosage of organic solvent is 50-150L；First part
Total dosage of initiator and second part initiator is 0.05-10mol, preferably 0.8-1.5mol；The dosage of crosslinking agent is 1-
40mol, preferably 10-20mol；The dosage of alkali is 10-200mol.
3. according to the method described in claim 1, wherein, the molar ratio between second part monomer M and first part monomer M is
0-100:100；
And/or the molar ratio between second part initiator and first part's initiator is 0-100:100.
4. according to the method described in claim 1, wherein, the organic solvent includes organic acid alkylester did；
And/or the initiator is selected from dibenzoyl peroxide, cumyl peroxide, di-tert-butyl peroxide, peroxidating
Lauroyl, peroxidized t-butyl perbenzoate, diisopropyl peroxydicarbonate, dicetyl peroxydicarbonate dicyclohexyl ester, azo
At least one of bis-isobutyronitrile and azobisisoheptonitrile；
And/or the crosslinking agent is that divinylbenzene and/or the esters of acrylic acid containing at least two esters of acrylic acid groups are handed over
Join agent, the structural formula of the esters of acrylic acid group are as follows:-O-C (O)-C (R ')=CH2, R ' is H or C1-C4Alkyl；It is preferred that
Ground, the crosslinking agent are selected from divinylbenzene, propandiols double methacrylate, propandiols double methyl methacrylate, ethylene glycol
Class double methacrylate, glycols double methyl methacrylate, trimethylolpropane trimethacrylate, trimethylol propane trimethyl
Acrylate, polyethyleneglycol diacrylate, polyethylene glycol double methyl methacrylate, O-phthalic acid diethylene glycol diacrylate
Ester, pentaerythritol tetraacrylate, five acrylate of dipentaerythrityl ether, six acrylate of dipentaerythrityl ether and ethoxylation
At least one of multi-functional degree acrylate；
And/or the alkali is selected from the hydroxide of metal and/or the acetate of metal；Preferably, the alkali is selected from hydroxide
Lithium, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, magnesium hydroxide, lithium acetate, sodium acetate, acetic acid
At least one of potassium, calcium acetate, barium acetate and zinc acetate.
5. method described in any one of -4 according to claim 1, wherein in step (1), maleic anhydride is contacted with monomer M
The condition reacted includes: inert atmosphere, and temperature is 50-90 DEG C, time 0.5-4h；
And/or in step (1), it is 50-90 DEG C that introduce the condition that the reaction was continued of the solution containing crosslinking agent, which include: temperature, and the time is
2-15h。
6. method described in any one of -4 according to claim 1, wherein introduce the side that the reaction was continued of the solution containing crosslinking agent
Formula are as follows: at 50-90 DEG C, the solution containing crosslinking agent is added dropwise to reaction system in 1-3h, is further continued for insulation reaction 1-4h.
7. method described in any one of -4 according to claim 1, wherein in step (2), the condition of the salinization includes:
Temperature is 20-100 DEG C, time 0.5-8h.
8. ionomer made from method described in any one of claim 1-7.
9. ionomer according to claim 8, wherein the dissolution of ionomer 30min in 5 times of weight, 50 DEG C of acetone
Object≤10 weight %；The mole of metal cation accounts for the structural unit A that maleic anhydride provides in ionomer in the ionomer
Integral molar quantity 10-100%；The degree of cross linking >=65% of the ionomer is 150-2000nm in microspheroidal and average grain diameter.
10. ionomer described in claim 8 or 9 is as nucleating agent in being modified to polyethylene terephthalate
Using.
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|---|---|---|---|---|
| US4511527A (en) * | 1982-12-16 | 1985-04-16 | Celanese Corporation | Alkali metal salts of cross-linked polymeric microgels as nucleating agents for polyethylene terephthalate molding compositions and method for molding |
| CN101880357A (en) * | 2010-07-09 | 2010-11-10 | 南京工业大学 | Polystyrene-graft-succinic carboxylic acid resin |
| CN102924641A (en) * | 2012-11-07 | 2013-02-13 | 复旦大学 | Nucleating agent of polyethylene glycol terephthalate and preparation method thereof |
| CN103145903A (en) * | 2013-03-11 | 2013-06-12 | 复旦大学 | Polyethylene terephthalate nucleating agent and preparation method thereof |
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2017
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4511527A (en) * | 1982-12-16 | 1985-04-16 | Celanese Corporation | Alkali metal salts of cross-linked polymeric microgels as nucleating agents for polyethylene terephthalate molding compositions and method for molding |
| CN101880357A (en) * | 2010-07-09 | 2010-11-10 | 南京工业大学 | Polystyrene-graft-succinic carboxylic acid resin |
| CN102924641A (en) * | 2012-11-07 | 2013-02-13 | 复旦大学 | Nucleating agent of polyethylene glycol terephthalate and preparation method thereof |
| CN103145903A (en) * | 2013-03-11 | 2013-06-12 | 复旦大学 | Polyethylene terephthalate nucleating agent and preparation method thereof |
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