CN109705251A - 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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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 ionomer contains structural unit B shown in structural unit A shown in formula (1), formula (2) and the cross-linked structure by crosslinking agent offer, wherein M1And M2It is each independently H or metal cation, R is H or methyl.The invention also discloses the methods for preparing ionomer and ionomer obtained by this method, which comprises by maleic anhydride, provides the monomer B of structural unit B shown in formula (2) and cross-linking agent reacts；In presence of water, products therefrom is reacted 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.
CN 102924641A discloses a kind of polyethylene terephthalate (PET) nucleating agent and preparation method thereof, should
The random copolymer or alternate copolymer that nucleating agent is styrene and maleic anhydride are through hydrolysis, salinization and purification benzene second obtained
Alkene/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 obtains
It is dissolved in Isosorbide-5-Nitrae-dioxane to copolymer, then by copolymer, alkali alcosol is added dropwise, the ionomer of generation is analysed from precipitating reagent
Out, it is filtered by vacuum, purification obtains styrene/maleic acid ionomer.PET crystallization temperature can be improved in the ionomer, accelerates crystallization speed
Rate.
CN 103145903A discloses a kind of polyethylene terephthalate (PET) nucleating agent and preparation method thereof, at
Core agent is poly- (styrene-alt- maleic anhydride) di-block copolymer of polystyrene-b- through made from hydrolysis, salinization and purification
Polystyrene-b- poly- (styrene-alt- maleic anhydride) two Block copolymer ionomers.The nucleating agent can form microfacies in PET melt
Separation, to provide nucleus for PET crystallization.
But ionomer 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
Ionomer and its preparation method and application, ionomer of the invention have good nucleating effect to PET.
To achieve the goals above, one aspect of the present invention provides a kind of microspheroidal ionomer with cross-linked structure, should
The cross-linked structure that ionomer contains structural unit B shown in structural unit A shown in formula (1), formula (2) and provided by crosslinking agent,
Wherein, M1And M2It is each independently H or metal cation, R is H or methyl.
Second aspect of the present invention provides a kind of method for preparing ionomer, this method comprises:
(1) in organic solvent, in the presence of initiator, by maleic anhydride, structural unit B shown in formula (2) is provided
Monomer B and cross-linking agent reacted；
(2) in presence of water, step (1) products therefrom is reacted with alkali and carries out salinization.
Third aspect present invention provides ionomer made from the method as described in second aspect.
Fourth 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 styrene/maleic acid sodium salt ionomer infrared spectrogram that comparative example 1 synthesizes；
Fig. 3 is the stereoscan photograph of the ionomer synthesized according to one embodiment of the present invention (embodiment 1).
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.
Microspheroidal ionomer provided by the invention with cross-linked structure contains structural unit A shown in formula (1), formula (2)
Shown in structural unit B and by crosslinking agent provide cross-linked structure,
Wherein, M1And M2It is each independently H or metal cation, R is H or methyl is (in ionomer, and not all structure
M in unit A1And M2It is to introduce to have metal cation in at least partly structural unit A of H namely the ionomer).
Wherein, the metal cation can be various common metal ions, for example, Li+、Na+、K+、Ca2+、Mg2+、
Ba2+Or Zn2+。
In the preferred embodiment of the present invention, the molar ratio between structural unit A and structural unit B is 100:(100-
120), more preferably 100:(100-105).
In another preferred embodiment of the invention, the molar ratio between structural unit A and cross-linked structure is 100:(1-
40), more preferably 100:(10-30).
In the present invention, according to a kind of preferred embodiment, the mole of metal cation is accounted for from poly- in the ionomer
In object the integral molar quantity of structural unit A 10-120% (such as 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%,
90%, the arbitrary value between 95%, 100%, 110%, 115%, 120% or above-mentioned numerical value).The degree of cross linking of the ionomer is excellent
Select >=65% (arbitrary value between such as 65%, 70%, 75%, 80%, 85%, 90% or above-mentioned numerical value).The ionomer is in
Microspheroidal and average grain diameter be 150-2000nm (such as 150nm, 250nm, 350nm, 450nm, 550nm, 650nm, 750nm,
850nm、950nm、1050nm、1150nm、1250nm、1350nm、1450nm、1550nm、1650nm、1750nm、1850nm、
Arbitrary value between 2000nm or above-mentioned numerical value).In the present invention, the molar content of metal cation passes through X-ray fluorescence spectra
It analyzes and obtains.The degree of cross linking indicates gel content, is measured by solvent extraction process.The average grain diameter is with number average bead diameter table
Sign, measures by scanning electron microscope.
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.
The method provided by the invention for preparing ionomer includes:
(1) in organic solvent, in the presence of initiator, by maleic anhydride, structural unit B shown in formula (2) is provided
Monomer B and cross-linking agent reacted；
(2) in presence of water, step (1) products therefrom is reacted with alkali and carries out salinization (or hydrolysis).
In step (1) of the invention, the dosage of each raw material used is not required particularly, it is preferable that relative to
The maleic anhydride of 100mol, the dosage of monomer B are 50-150mol, more preferably 75-100mol.Those skilled in the art can
Understand, maleic anhydride is to provide the substance of structural unit A shown in formula (1).Monomer B is to provide structure shown in formula (2)
The substance of unit B can be α-methylstyrene or styrene.
Preferably, relative to the maleic anhydride of 100mol, the dosage of crosslinking agent is 1-40mol, more preferably 10-20mol,
Further preferably 15-20mol.
Preferably, relative to the maleic anhydride of 100mol, the dosage of organic solvent is 50-150L, more preferably 75-
100L。
Preferably, relative to the maleic anhydride of 100mol, the dosage of initiator is 0.05-10mol, more preferably 1-
1.5mol。
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 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 step (1) of the invention, the specific type of the crosslinking agent is as previously mentioned, details are not described herein.
In step (1) of the invention, the condition of the reaction is not required particularly, but under preferable case, it is described anti-
The condition answered makes the degree of cross linking >=65% of ionomer.It is highly preferred that the condition of the reaction includes: indifferent gas in step (1)
Atmosphere, temperature are 50-90 DEG C (further preferably 60-70 DEG C), and the time is 3-15h (further preferably 5-12h).
According to the method for the present invention, in step (2), 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 in above range
It is interior.The dosage of the alkali can be conventional selection, it is preferable that relative to the maleic anhydride of 100mol, the dosage of the alkali is 10-
200mol (arbitrary value between such as 10mol, 50mol, 100mol, 150mol, 190mol, 200mol or above-mentioned numerical value).It is described
Alkali preferably uses in form of an aqueous solutions, 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, molar ratio, the degree of cross linking and average grain diameter between metal cation content, each structural unit etc. as previously mentioned,
This is repeated no more.
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 100g, α-methylstyrene 118g, divinylbenzene 26g, azodiisobutyronitrile 2g are dissolved in
In 1000mL isoamyl acetate, under nitrogen atmosphere, reacted 5 hours at 70 DEG C.System after reaction exists through centrifuge
Be centrifugated 30 minutes under the conditions of 5000rad/min, obtain crosslinking α-methylstyrene/maleic anhydride polymer microballoon, just oneself
Alkane washing purifying, vacuum drying.
Meanwhile the supernatant after centrifuge separation is analyzed through LC-MC, wherein remaining amount of monomer is measured, with the monomer of investment
Amount (or cross-linked dosage) subtracts remaining amount of monomer (or cross-linked dosage) and obtains amount of monomer (or the crosslinking agent of actual participation reaction
Amount), so that the molar ratio between structural unit A, structural unit B and cross-linked structure is obtained, (similarly hereinafter, one shown in table 1 specific as follows
When pot method preparation, supernatant is taken to measure amount of monomer after taking a small amount of organic phase centrifugation to separate).
(2) sodium hydroxide 15.2g is dissolved in 350mL water, will be crosslinked α-methylstyrene/maleic anhydride polymer microballoon
50g is added in sodium hydrate aqueous solution (relative to every mole of maleic anhydride, the dosage of alkali is 1.9mol), anti-at 100 DEG C
It answers 3 hours.System after reaction is centrifugated 30 minutes under the conditions of 5000rad/min through centrifuge, and solid adds 400mL water to stir
Mix washing, be centrifugated 30 minutes under the conditions of 5000rad/min through centrifuge, solid adds 500mL methanol agitator treating, through from
Scheming is centrifugated 30 minutes under the conditions of 5000rad/min, and solid vacuum drying obtains crosslinking α-methylstyrene/Malaysia
Acid sodium-salt ionomer microballoon (being denoted as C1).
Embodiment 2
The present embodiment is used to illustrate ionomer microballoon and preparation method thereof of the invention.
(1) maleic anhydride 100g, α-methylstyrene 118g, divinylbenzene 26g, azodiisobutyronitrile 2g are dissolved in
In 1000mL isoamyl acetate, under nitrogen atmosphere, reacted 5 hours at 70 DEG C.System after reaction exists through centrifuge
It is centrifugated 30 minutes under the conditions of 5000rad/min, obtains crosslinking α-methylstyrene/maleic anhydride polymer microballoon, methanol
Washing purifying, vacuum drying.
(2) sodium acetate 20.5g is dissolved in 300mL water, will be crosslinked α-methylstyrene/maleic anhydride polymer microballoon 50g
It is added in sodium acetate aqueous solution (relative to every mole of maleic anhydride, the dosage of alkali is 1.2mol), it is small that 4 is reacted at 100 DEG C
When.System after reaction is centrifugated 30 minutes under the conditions of 5000rad/min through centrifuge, and solid adds the stirring of 400mL water to wash
It washs, is centrifugated 30 minutes under the conditions of 5000rad/min through centrifuge, solid adds 500mL methanol agitator treating, through centrifuge
It is centrifugated 30 minutes under the conditions of 5000rad/min, solid vacuum drying obtains crosslinking α-methylstyrene/sodium maleate
Salt ionomer microballoon (being denoted as C2).
Embodiment 3
The present embodiment is used to illustrate ionomer microballoon and preparation method thereof of the invention.
(1) maleic anhydride 100g, α-methylstyrene 118g, divinylbenzene 26g, azodiisobutyronitrile 2g are dissolved in
In 1000mL isoamyl acetate, under nitrogen atmosphere, reacted 5 hours at 70 DEG C.System after reaction exists through centrifuge
It is centrifugated 30 minutes under the conditions of 5000rad/min, obtains crosslinking α-methylstyrene/maleic anhydride polymer microballoon, methanol
Washing purifying, vacuum drying.
(2) zinc acetate 36.7g is dissolved in 400mL water, will be crosslinked α-methylstyrene/maleic anhydride polymer microballoon 50g
It is added in zinc acetate aqueous solution (relative to every mole of maleic anhydride, the dosage of alkali is 1mol), is reacted 8 hours at 100 DEG C.
System after reaction is centrifugated 30 minutes under the conditions of 5000rad/min through centrifuge, and solid adds 400mL water agitator treating,
It is centrifugated 30 minutes under the conditions of 5000rad/min through centrifuge, solid adds 500mL methanol agitator treating, exists through centrifuge
It is centrifugated 30 minutes under the conditions of 5000rad/min, solid vacuum drying obtains crosslinking α-methylstyrene/maleic acid zinc salt
Ionomer microballoon (is denoted as C3).
Embodiment 4
The present embodiment is used to illustrate ionomer microballoon and preparation method thereof of the invention.
(1) maleic anhydride 130g, α-methylstyrene 118g, divinylbenzene 26g, azodiisobutyronitrile 2.5g are dissolved in
In 1000mL isoamyl acetate, under nitrogen atmosphere, reacted 12 hours at 60 DEG C.System after reaction exists through centrifuge
It is centrifugated 30 minutes under the conditions of 5000rad/min, obtains crosslinking α-methylstyrene/maleic anhydride polymer microballoon, methanol
Washing purifying, vacuum drying.
(2) one hydronium(ion) lithia 15.6g are dissolved in 450mL water, will be crosslinked α-methylstyrene/maleic anhydride polymer
Microballoon 50g is added in lithium hydroxide aqueous solution (relative to every mole of maleic anhydride, the dosage of alkali is 1.85mol), and 100 DEG C
Lower reaction 3 hours.System after reaction is centrifugated 30 minutes under the conditions of 5000rad/min through centrifuge, and solid adds 400mL
Water agitator treating is centrifugated 30 minutes under the conditions of 5000rad/min through centrifuge, and solid adds 500mL methanol agitator treating,
Be centrifugated 30 minutes under the conditions of 5000rad/min through centrifuge, solid vacuum drying, obtain crosslinking α-methylstyrene/
Maleic acid lithium salts ionomer microballoon (being denoted as C4).
Embodiment 5
The present embodiment is used to illustrate ionomer microballoon and preparation method thereof of the invention.
(1) maleic anhydride 130g, α-methylstyrene 118g, divinylbenzene 26g, azodiisobutyronitrile 2.5g are dissolved in
In 1000mL isoamyl acetate, under nitrogen atmosphere, reacted 12 hours at 60 DEG C.System after reaction exists through centrifuge
It is centrifugated 30 minutes under the conditions of 5000rad/min, obtains crosslinking α-methylstyrene/maleic anhydride polymer microballoon, methanol
Washing purifying, vacuum drying.
(2) potassium hydroxide 15.0g is dissolved in 400mL water, will be crosslinked α-methylstyrene/maleic anhydride polymer microballoon
50g is added in potassium hydroxide aqueous solution (relative to every mole of maleic anhydride, the dosage of alkali is 1.3mol), is reacted at 30 DEG C
3 hours.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
Sylvite ionomer microballoon (being denoted as C5).
Embodiment 6
The present embodiment is used to illustrate ionomer microballoon and preparation method thereof of the invention.
(1) maleic anhydride 100g, styrene 104g, divinylbenzene 26g, azodiisobutyronitrile 2.5g are dissolved in 1000mL second
In isoamyl valerate, under nitrogen atmosphere, reacted 12 hours in 60 DEG C of water-bath.System after reaction is through centrifuge in 5000rad/
It is centrifugated 30 minutes under the conditions of min, obtains cross-linked styrene/maleic anhydride polymer microballoon, methanol washing purifying, vacuum are dry
It is dry.
(2) sodium hydroxide 13.5g is dissolved in 350mL water, and cross-linked styrene/maleic anhydride polymer microballoon 50g is added
To in sodium hydrate aqueous solution (relative to every mole of maleic anhydride, the dosage of alkali is 1.6mol), reacted 3 hours at 100 DEG C.
System after reaction is centrifugated 30 minutes under the conditions of 5000rad/min through centrifuge, and solid adds 400mL water agitator treating,
It is centrifugated 30 minutes under the conditions of 5000rad/min through centrifuge, solid adds 500mL methanol agitator treating, exists through centrifuge
It is centrifugated 30 minutes under the conditions of 5000rad/min, solid vacuum drying obtains cross-linked styrene/maleic acid sodium salt ionomer
Microballoon (is denoted as C6).
Embodiment 7
The present embodiment is used to illustrate ionomer microballoon and preparation method thereof of the invention.
(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 into the system after step (1) reaction, reacts 3 at 80 DEG C
Hour.System stratification after reaction, heavy phase are centrifugated 20 minutes under the conditions of 5000rad/min through centrifuge, solid
Adding 4L water agitator treating, is centrifugated 20 minutes under the conditions of 5000rad/min through centrifuge, solid adds 4L water agitator treating,
Be centrifugated 20 minutes under the conditions of 5000rad/min through centrifuge, solid vacuum drying, obtain crosslinking α-methylstyrene/
Maleic acid sodium salt ionomer microballoon (being denoted as C7).
(3) system after step (1) reaction is centrifugated 30 minutes under the conditions of 5000rad/min through centrifuge, is obtained
To crosslinking α-methylstyrene/maleic anhydride polymer microballoon, solvent washing purifying, vacuum drying.Add sodium hydroxide water
(10wt%, relative to every mole of maleic anhydride, the dosage of alkali is 1.25mol) to solution 3500g, is reacted 3 hours at 80 DEG C.Instead
System after answering is centrifugated 30 minutes under the conditions of 5000rad/min through centrifuge, and solid adds 400mL water agitator treating, warp
Centrifuge is centrifugated 30 minutes under the conditions of 5000rad/min, and solid adds 500mL methanol agitator treating, is existed through centrifuge
It is centrifugated 30 minutes under the conditions of 5000rad/min, solid vacuum drying obtains crosslinking α-methylstyrene/maleic acid sodium salt
Ionomer microballoon (is denoted as C7-1).
Embodiment 8
The present embodiment is used to illustrate ionomer microballoon and preparation method thereof of the invention.
(1) by maleic anhydride 1000g, α-methylstyrene 1180g, ethylene glycol dimethacrylate 600g, azo two
Different heptonitrile 25g is dissolved in 15L isoamyl acetate, under nitrogen atmosphere, is reacted 5 hours at 70 DEG C.
(2) lithium hydroxide aqueous solution 1000g (10wt%) is added after reacting, is reacted 0.5 hour at 90 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 crosslinking α-methylstyrene/maleic acid lithium salts
Ionomer microballoon (is denoted as C8).
Embodiment 9
Prepare ionomer microballoon according to the method for embodiment 1, unlike, the dosage of divinylbenzene is 10g, obtain from
Polymers microballoon C9.
Comparative example 1
(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-D1).
Test case 1
(1) infrared spectrum analysis is carried out to the polymer that embodiment 1 and comparative example 1 obtain, as a result respectively such as Fig. 1 and Fig. 2
It is shown, from results of IR it can be seen that ionomer successfully synthesizes, the results of IR and reality of embodiment 2-9
It is similar to apply example 1, has successfully obtained ionomer.
(2) the ionomer microballoon prepared in above-described embodiment is subjected to X-ray fluorescence spectra analysis, to measure ionomer
In metal cation content, that is, account for the percentage of the integral molar quantity of structural unit A in ionomer.
(3) ionomer prepared in above-described embodiment and comparative example is scanned Electronic Speculum detection, wherein embodiment 1 obtains
The scanning electron microscope (SEM) photograph of the ionomer obtained is fig. 3, it is shown that ionomer of the invention is in microspheroidal；And comparative example 1 obtains
Ionomer do not have micro-sphere structure.The average grain diameter and the degree of cross linking for measuring ionomer microballoon (partial size test method: are shone in Electronic Speculum
500 microballoons are chosen in piece, measure its diameter, the average grain diameter of microballoon is calculated with mathematic(al) mean method；Degree of cross linking measuring method:
2-3 grams of polymer microballoon (w1) is weighed, is wrapped using middling speed qualitative filter paper, is put into Soxhlet extractor, extracted using tetrahydrofuran
24 hours, the degree of cross linking was calculated by w2/w1 in the dry weighing w2 of polymer) etc. it is 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 | 127.3 | 204.8 | 5.3 | -36.7 |
| C2 modified PET | 130.2 | 202.3 | 6.5 | -34.6 |
| C3 modified PET | 128.6 | 201.3 | 5.8 | -35.1 |
| C4 modified PET | 129.3 | 200.8 | 6.3 | -33.8 |
| C5 modified PET | 130.5 | 199.5 | 7.2 | -35.0 |
| C6 modified PET | 128.8 | 203.0 | 6.1 | -34.8 |
| C7 modified PET | 129.5 | 202.2 | 6.4 | -36.8 |
| C7-1 modified PET | 130.7 | 200.8 | 6.6 | -36.6 |
| C8 modified PET | 132.8 | 195.5 | 9.5 | -32.7 |
| C9 modified PET | 131.7 | 196.3 | 8.9 | -32.8 |
| C-D1 modified PET | 134.7 | 195.2 | 10.2 | -35.0 |
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；In addition, compared to not having microballoon knot
The non-crosslinked α-methylstyrene of structure/maleic acid sodium salt ionomer has more preferably nucleating effect to PET.
In addition, comparing embodiment 1 and embodiment 8-9 can be seen that the dosage for controlling crosslinking agent etc. energy in preferred scope
It is enough to 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
2 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 118-145MPa
In range, elongation at break is about 2%, and bending strength is within the scope of 140-180MPa, and bending modulus is in 5.6-9.5GPa range
Interior, simply supported beam notch impact strength is in 4.5-10kJ/m2In range, it is placed in 2 hours in 120 DEG C of baking ovens and does not observe apparent change
Shape.
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 (11)
1. a kind of microspheroidal ionomer with cross-linked structure, which is characterized in that the ionomer contains structure list shown in formula (1)
Structural unit B shown in first A, formula (2) and the cross-linked structure provided by crosslinking agent,
Wherein, M1And M2It is each independently H or metal cation, R is H or methyl.
2. ionomer according to claim 1, wherein mole between structural unit A, structural unit B and cross-linked structure
Than for 100:100-120:1-40, preferably 100:100-105:10-30.
3. ionomer according to claim 1, wherein the mole of metal cation accounts in ionomer in the ionomer
The 10-120% of the integral molar quantity of structural unit A；The degree of cross linking >=65% of the ionomer, average grain diameter 150-2000nm.
4. ionomer according to claim 1, wherein the crosslinking agent is divinylbenzene and/or contains at least two
The acrylic ester cross-linking agent of esters of acrylic acid group, 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；
Preferably, the crosslinking agent is selected from divinylbenzene, propandiols double methacrylate, propandiols methacrylate
Ester, glycols double methacrylate, glycols double methyl methacrylate, trimethylolpropane trimethacrylate, trihydroxy methyl
Propane trimethyl acrylic ester, polyethyleneglycol diacrylate, polyethylene glycol double methyl methacrylate, phthalic acid diethyl two
Alcohol diacrylate, pentaerythritol tetraacrylate, five acrylate of dipentaerythrityl ether, six acrylate of dipentaerythrityl ether
At least one of with the multi-functional degree acrylate of ethoxylation.
5. a kind of method for preparing ionomer, which is characterized in that this method comprises:
(1) in organic solvent, in the presence of initiator, by maleic anhydride, the list of structural unit B shown in formula (2) is provided
Body B and cross-linking agent are reacted；
(2) in presence of water, step (1) products therefrom is reacted with alkali and carries out salinization.
6. according to the method described in claim 5, wherein, relative to the maleic anhydride of 100mol, the dosage of monomer B is 50-
150mol, preferably 75-100mol；The dosage of crosslinking agent is 1-40mol, preferably 10-20mol；The dosage of organic solvent is
50-150L, preferably 75-100L；The dosage of initiator is 0.05-10mol, preferably 1-1.5mol；The dosage of alkali is 10-
200mol。
7. method according to claim 5 or 6, 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.
8. according to the method described in claim 5, wherein, in step (1), the condition of the reaction makes the degree of cross linking of ionomer
>=65%；
Preferably, in step (1), the condition of the reaction includes: inert atmosphere, and temperature is 50-90 DEG C, time 3-15h.
9. the method according to claim 5 or 8, wherein in step (2), the condition of the salinization includes: that temperature is 20-
100 DEG C, time 0.5-8h.
10. ionomer made from method described in any one of claim 5-9.
11. ionomer described in any one of claim 1-4 and 10 is as nucleating agent to polyethylene terephthalate
Ester be modified in application.
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| CN201711016466.0A CN109705251B (en) | 2017-10-25 | 2017-10-25 | Microspherical ionomer with cross-linked structure and preparation method and application thereof |
| JP2020523424A JP7154291B2 (en) | 2017-10-25 | 2018-10-25 | Microspherical ionomer having crosslinked structure, its production method, its use, and its production system |
| TW107137774A TWI785136B (en) | 2017-10-25 | 2018-10-25 | Microspherical ionomer with crosslinked structure, preparation method, application and preparation system thereof |
| EP18871366.3A EP3702384A4 (en) | 2017-10-25 | 2018-10-25 | Microspheric ionomer having cross-linking structure, preparation method therefor, applications thereof, and preparation system thereof |
| KR1020207014615A KR102522818B1 (en) | 2017-10-25 | 2018-10-25 | Microspherical ionomer with a cross-linked structure, its preparation method, its use and production system |
| US16/758,839 US11965089B2 (en) | 2017-10-25 | 2018-10-25 | Microspheric ionomer having cross-linked structure, preparation method therefor, applications thereof, and preparation system thereof |
| PCT/CN2018/111825 WO2019080891A1 (en) | 2017-10-25 | 2018-10-25 | Microspheric ionomer having cross-linking structure, preparation method therefor, applications thereof, and preparation system thereof |
| US18/604,473 US20240270958A1 (en) | 2017-10-25 | 2024-03-13 | Microspheric ionomer having cross-linked structure, preparation method therefor, applications thereof, and preparation system thereof |
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