CN106866636B - Imide β crystal form nucleating agent, and preparation method and application thereof - Google Patents
Imide β crystal form nucleating agent, and preparation method and application thereof Download PDFInfo
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- CN106866636B CN106866636B CN201611228551.9A CN201611228551A CN106866636B CN 106866636 B CN106866636 B CN 106866636B CN 201611228551 A CN201611228551 A CN 201611228551A CN 106866636 B CN106866636 B CN 106866636B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
- C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
- C08L2205/242—Beta spherulite nucleating agents
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Abstract
The invention discloses an imide β crystal form nucleating agent, a preparation method and an application thereof, wherein the nucleating agent has the following structure (I):
wherein R is
1，R
2，R
3The invention also discloses a preparation method of the imide β crystal form nucleating agent, wherein melamine, an acylation reagent and a catalyst are heated to react, and then are cooled, filtered and purified to obtain the imide β crystal form nucleating agent which is mild in reaction condition, simple and environment-friendly in process and easy for industrial production, and the produced imide polyolefin β crystal form nucleating agent is efficient and environment-friendly.
Description
Technical field
The present invention relates to a kind of beta crystal-type nucleaters more particularly to a kind of sub- amides beta crystal-type nucleater and preparation method thereof
With application.
Background technique
Nucleating agent is to refer to changing section crystallization behavior, and raising product transparency, rigidity, lustrous surface, shock resistance are tough
Property and heat distortion temperature, shorten the product molding period, improve product processing and application performance functional form chemical assistant, nucleating agent
Suitable for polymer of polymer, especially imperfect crystal, such as polyethylene, polypropylene etc..
Beta crystal-type nucleater is that one kind can generate in process high level beta crystal state of aggregation knot with induced polymer
The additive of structure.It acts on the impact strength and heat distortion temperature for mainly improving product.Beta crystal-type nucleater be divided into it is organic and
Inorganic two major classes.Organic mainly has condensed-nuclei aromatics class (dye class), organic acid and salt and amides.Inorganic mainly whether there is or not
Machine salt, inorganic oxide and some metal powder with low melting point.Condensed-nuclei aromatics class nucleating agent structure is more complex, is nucleated performance
It is good, but because belonging to dye class, product is colored and influences its application range.Organic acid and its esters fusing point are high, heat-resist, but this
Kind of nucleating agent due to organic carboxyl acid decomposed, the precipitate easy to form in forming process and influence service efficiency and product matter
Amount.Amides beta crystal-type nucleater is based on sub- amides compound, especially substituted benzene Asia amides compound, such nucleation
Agent nucleation efficiencies are high, but synthesis cost is higher.Inorganic nucleating agent is cheap, but nucleation efficiencies are low, and influences the transparency, limit
Its application in high performance material is made.Currently used beta crystal-type nucleater is mainly based on amides and terres rares.
Alpha-crystal form polypropylene can be made to be converted into β since γ crystal form dyestuff quinacridone was added in discovery in 1967 in Leugering
Since crystal form, is in the world expanded to the research of beta crystal-type nucleater more than 40 years.Nineteen ninety-five, Wolfschwenger
Johannes et al. obtains Beta-crystalline polyacrylic using a kind of pimelate nucleating agent in polyacrylic granulation process, still
The nucleater modified effect is unobvious, and crystallization temperature does not significantly improve, and declines bending modulus instead, simultaneously because having
Part dicarboxylate is thermally decomposed, so that forming precipitating in the final product.On this basis, A.L shellfish is gloomy et al. uses imido
Acid is reacted with containing the Group IIA metal fatty acid salt in the periodic table of elements, prepares beta crystal-type nucleater.US 6235823B1 is disclosed
The method for preparing amides polypropylene beta crystal nucleating agent by dicarboxylic acids and monoamine, this method are included in atent solvent,
It reacts dicarboxylic acids and monoamine 2-8 hours, accelerates to react in the reaction using activator, however, passing through experiment hair
It is existing, amides polypropylene beta crystal nucleating agent is prepared using above-mentioned patented method and needs to be reacted under high pressure, thus it is right
Production equipment has very high requirement, to not can be carried out large-scale industrial production.Along in the world for beta crystal nucleation
The research boom of agent, China also continue to bring out new product in recent years, and 1986, history saw first-class in DE-A-3610644, EP
0682066, the salt of certain group iia elements disclosed in the patents such as CN 1004076B or its answering with specific dicarboxylic acids
Object or compound are closed, typical example is calcium stearate/pimelic acid compound or calcium pimelate.EP 0887475,CN
The salt formed in 1210103 with group iia category element in imidic acid and periodic table, 2002, the bright woods in Guangdong was taken in the fresh material supply section
Skill limited liability company and Guangzhou Inst of Chemistry, Chinese Academy of Sciences have developed a kind of mixed matching rare earth beta crystal-type nucleater cooperatively
WBG, and be published in Chinese patent ZL00117339, when 0.15% WBG is added, beta crystal content reaches 90% in polypropylene
More than, not only nucleation efficiencies are high, but also color is in bright milky, and stability, nucleation selectivity etc. have apparent advantage.
China Textile University has studied beta crystal-type nucleater to beta crystal structure in polypropylene spinning technique and as-spun fibre
It influences.Nanjing University of Chemical Technology is nucleated in homopolypropylene and copolymer polypropylene system with homemade beta crystal-type nucleater
Agent additive amount and Mechanical Properties of PP correlation research.Chinese Academy of Sciences's Shanghai Institute of Organic Chemistry has prepared β with pimelic acid and calcium stearate
Crystal-type nucleater has studied influence of the beta crystal-type nucleater content to crystalling propylene and melting behavior.The Shanxi on commercial product
Chemical institute, which develops efficient β crystalline substance nucleating agent (substituted aromatic amide class) beta crystal, can reach 90%, Lyu of Institutes Of Technology Of Taiyuan
Will equality discloses a kind of dicarboxylate polypropylene beta crystal nucleating agent in Chinese patent CN101418084A, which can
Effectively to induce the formation of polypropylene beta crystal.In addition, disclosing tetrahydrophthalic acid in Chinese patent CN102181092A
Barium, carboxylic acid metal's salt compound of the tetrahydrophthalic anhydride such as tetrahydrophthalic acid calcium is as polypropylene beta crystal nucleating agent.
In order to reduce cost and improve the nucleation efficiencies of beta crystal-type nucleater, CN101157771B and CN101580601A are public
The method opened and first loaded dicarboxylic acids, and then prepared beta crystal-type nucleater.CN101619143B discloses a kind of fibre
Dimension load beta crystal-type nucleater makes the polypropylene composite materials of preparation using the excellent toughness of enhancing function and the β crystalline substance of fibrous material
Material is not while intensity and modulus reduces, hence it is evident that improves the toughness and ductility of material.Above-mentioned support type beta crystal-type nucleater
It is the expanded application of the beta crystal-type nucleater about organic acid and salt.For other class beta crystal-type nucleaters, due to its structure
Upper to lack reactive active group, further modification application is restricted.Although beta crystal-type nucleater have it is very high at
Core efficiency and industrialized production is realized, but compared with common crystal-type nucleater, beta crystal-type nucleater type is few and price is high
It is expensive, beta crystal-type nucleater efficiently, inexpensive is found, is still the highly important research direction in the field.
Summary of the invention
The main purpose of the present invention is to provide a kind of sub- amides beta crystal-type nucleaters and the preparation method and application thereof, should
Method reaction condition is mild, simple process environmental protection, easy to industrialized production, the sub- amides polyolefin beta crystal-type nucleater of production
It is efficiently and environmentally friendly.
To achieve the goals above, the present invention provides a kind of sub- amides beta crystal-type nucleater, which has as follows
Formula (I) structure:
Wherein, R1, R2And R3It is independent selected from H, halogen, the alkyl of 1~10 carbon, 6~10 carbon aryl and 6~10
Group composed by the aryl derivatives of a carbon.
Asia amides beta crystal-type nucleater of the present invention, wherein the alkyl of 1~10 carbon is preferably methyl, second
Base, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, n-hexyl or isohesyl；Institute
The aryl for stating 6~10 carbon is preferably single-substituted or disubstituted benzene, and the substituent group is the alkyl of 0~4 carbon；Described 6~
The aryl derivatives of 10 carbon are preferably single-substituted or disubstituted benzene, and the substituent group is the alkoxy of 0~4 carbon.
To achieve the goals above, the present invention also provides the preparation method of above-mentioned sub- amides beta crystal-type nucleater, the party
Method includes the following steps:
Melamine is added in solvent step 1, then lower that acylating reagent and catalyst is added, it is stirred at room temperature 0.5~
After 5h, be heated to 80~160 DEG C reaction 10~for 24 hours, wherein the molar ratio of melamine, acylating reagent and catalyst be 1:1.05
~1.3:0.1~0.35, preferably 1:1.15:0.2；And
Step 2 cools to room temperature, and white precipitate is obtained by filtration, and washing is dried to obtain sub- amides beta crystal-type nucleater；
Wherein, the acylating reagent is mono-substituted phthalic anhydride, mono-substituted phthalic acid, mono-substituted neighbour
One or more of phthalyl chloride and mono-substituted the formed group of O-phthalic acylbromide, wherein substituent group is H, halogen, 1
Group composed by the aryl derivatives of the alkyl of~10 carbon, the aryl of 6~10 carbon and 6~10 carbon.
The preparation method of Asia amides beta crystal-type nucleater of the present invention, wherein the alkyl of 1~10 carbon is excellent
It is selected as methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl, n-hexyl
Or isohesyl；The aryl of 6~10 carbon is preferably single-substituted or disubstituted benzene, and the substituent group is the alkane of 0~4 carbon
Base；The aryl derivatives of 6~10 carbon are preferably single-substituted or disubstituted benzene, and the substituent group is the alkane of 0~4 carbon
Oxygroup.
The preparation method of Asia amides beta crystal-type nucleater of the present invention, wherein the catalyst is preferably methylamine,
Urea (urea), ethanol amine, ethylenediamine, triethylamine, isopropylamine, aniline, benzylamine, triethylene diamine (DABCO), diazabicylo
(DBU), to dimethylamino naphthyridine (DMAP), pyridine, N-methylmorpholine, in tetramethylethylenediamine and the formed group of potassium tert-butoxide
One kind, further preferably to dimethylamino naphthyridine.
The preparation method of Asia amides beta crystal-type nucleater of the present invention, wherein the solvent is preferably N, N- diformazan
One or more of base formamide, pyridine, dimethyl sulfoxide, water and the formed group of N-Methyl pyrrolidone, it is further excellent
It is selected as water.
The preparation method of Asia amides beta crystal-type nucleater of the present invention, wherein the step 1 heating temperature is preferred
It is 100~120 DEG C, the reaction time is preferably 10~14h.
The present invention also provides application of the above-mentioned sub- amides beta crystal-type nucleater in imperfect crystal polymer arts.
Beneficial effects of the present invention:
The present invention provides a kind of methods for synthesizing sub- amides compound, mainly using melamine as raw material, then
By the investigation of the combined systems such as suitable catalyst, solvent, to realize the efficient of melamine Asia amides compound
Synthesis, this method reaction condition is mild, simple process environmental protection, easy to industrialized production, the sub- amides polyolefin beta crystal of production
Nucleating agent is efficiently and environmentally friendly.
Specific embodiment
Elaborate below to the embodiment of the present invention: the present embodiment carries out under the premise of the technical scheme of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
For the present invention to the dosage of solvent there is no stringent limitation, those skilled in the art can according to real reaction and just
Control in post-processing.
Method of the invention is illustrated below by specific embodiment, but the present invention is not limited thereto.
Experimental method described in following embodiments is unless otherwise specified conventional method；The reagent and material, such as
Without specified otherwise, commercially obtain.
Embodiment 1:
Concrete operations are as follows: weigh 1.26g melamine (10mmol) and be added in the two mouth flask of 100mL, then plus
Enter 50mL water, mixture is slowly stirred to obtain white suspension.0.24g is then slowly added into dimethylamino naphthyridine, reaction mixing
Object continues that 30min is stirred at room temperature, and is then slowly added into 4.5g phthalic anhydride (30mmol), is then slowly added with oil bath
Heat stops heating to 90 DEG C of the reaction was continued 14h, and reaction continues to be kept stirring, and drops to room temperature to temperature.
Post-processing: after cooling to room temperature, having a large amount of white solids to be precipitated, and white solid is obtained by filtration, solid phase is with largely
Then water washing is washed with organic solvent-normal hexane again, solid is dry to obtain the formula (I) compound 4.31g (yield
83%).
Nuclear magnetic data:
1H-NMR(400MHz,CDCl3) δ: 7.54 (d, J=7.8Hz, 6H), 7.02 (d, J=7.8Hz, 6H) .MS (EI):
m/z 516(M+)。
Embodiment 2:
Change the reaction time in embodiment 1, the reaction time is changed to 10h, and other conditions and embodiment 1 are just the same, knot
Fruit obtains final products 3.94g (yield 76.3%)；It is extended between when reacted for 24 hours, the final products 4.30g (yield of reaction
82.5%).
Embodiment 3:
Change the reaction temperature in embodiment 1, reaction temperature is changed to 60 DEG C, and other conditions and embodiment 1 are just the same, knot
Fruit does not obtain final products, and raw material does not almost participate in reaction；After reaction temperature is increased to 100 DEG C, final products are reacted to obtain
4.13g (yield 80%).
Embodiment 4:
Change the catalyst amount in embodiment 1, melamine and catalyst amount ratio are 1:0.01, other conditions and reality
It is just the same to apply example 1, as a result obtains final products 2.1g (yield 40.7%)；Increase catalyst dosage, melamine with urge
Agent amount ratio 1:0.35 obtains final products 4.32g (82.7%).
Embodiment 5:
Concrete operations are as follows: weigh 1.26g melamine (10mmol) and be added in the two mouth flask of 100mL, then plus
Enter 50mL water, mixture is slowly stirred to obtain white suspension.0.24g is then slowly added into dimethylamino naphthyridine, it is anti-after adding
It answers mixture to continue that 2h is stirred at room temperature, is then slowly added into 6.9g 4- phthalate bromine acid anhydride (30mmol), then with oil
Bath is heated slowly to 110 DEG C, and the reaction was continued 14 hours, stops heating, and reaction continues to be kept stirring, and drops to room temperature to temperature.
Post-processing: cooling to room temperature, has a large amount of white solids to be precipitated, white solid, a large amount of water of solid phase are obtained by filtration
Washing, is then washed with organic solvent-normal hexane again, and solid is dry to obtain the type I compound 4.7g (yield 63%).
Nuclear magnetic data:
1H-NMR(400MHz,CDCl3) δ: 8.30 (d, J=2.4,3H), 7.89 (m, 3H), 7.64 (d, J=7.8Hz,
3H),MS(EI):m/z 750(M+).
Embodiment 6:
Concrete operations are as follows: weigh 1.26g melamine (10mmol) and be added in the two mouth flask of 100mL, then plus
Enter 50mL water, mixture is slowly stirred to obtain white suspension.0.25g is then slowly added into triethylamine, reaction mixture continues
5h is stirred at room temperature, is then slowly added into 4.5g phthalic anhydride (30mmol), is then heated slowly to 100 DEG C with oil bath
The reaction was continued 14h stops heating, and reaction continues to be kept stirring, and drops to room temperature to temperature.
Post-processing: after cooling to room temperature, having a large amount of white solids to be precipitated, and white solid is obtained by filtration, solid phase is with largely
Then water washing is washed with organic solvent-normal hexane again, solid is dry to obtain the formula (I) compound 3.95g (yield
76.5%).
Nuclear magnetic data:
1H-NMR(400MHz,CDCl3) δ: 7.54 (d, J=7.8Hz, 6H), 7.02 (d, J=7.8Hz, 6H) .MS (EI):
m/z 516(M+)。
Embodiment 7:
Concrete operations are as follows: weighing 0.252g melamine (2mmol) and are added in the two mouth flask of 50mL, are then added
25mL is dry n,N-Dimethylformamide (DMF), and ice-water bath cools to 5 DEG C, and 0.5g triethylamine is added in mixture, then slowly adds
Enter the adjacent dibenzoyl chlorine of 1.3g (6.4mmol), adds rear reaction mixture and be warming up to and stir 30min at room temperature, then use oil bath
Being heated slowly to 90 DEG C, the reaction was continued 10 hours, stops heating, and reaction continues to be kept stirring, and drops to room temperature to temperature.
Post-processing: after cooling to room temperature, there is a small amount of white powder to be precipitated, be removed by filtration white powder, then organic addition
Enter a large amount of water, there are a large amount of white solids to be precipitated, white solid is obtained by filtration, then solid phase is washed with massive laundering, is then used again
Organic solvent-normal hexane washing, solid are dry to obtain the formula (I) compound 0.46g (yield 44.6%).
Nuclear magnetic data:
1H-NMR(400MHz,CDCl3) δ: 7.54 (d, J=7.8Hz, 6H), 7.02 (d, J=7.8Hz, 6H) .MS (EI):
m/z 516(M+)。
The preparation of Beta-crystalline polyacrylic
(1) polypropylene is blended with antioxidant: isotactic polypropylene pellet (Guangxi petrochemical industry L5D98) 200g, antioxidant 1010
0.4g (2000ppm) is sufficiently mixed uniformly.(2) into step (1) pretreated isotactic polypropylene respectively according to 0,0.02,
0.04,0.06,0.08,0.1,0.15, the sub- amides beta crystal-type nucleater that embodiment 1 is prepared is added in 0.3wt% ratio,
It is sufficiently mixed in mixing machine, is dried in air dry oven, isotactic polypropylene powder be blended is separately added into twin-screw extrusion
The hopper of machine (draw ratio 42:1), (wherein, the temperature of each warm area of extruder is respectively as follows: an area 160 in 160-210 DEG C
DEG C, 180 DEG C of 2nd area, 190 DEG C of 3rd area, 200 DEG C of 4th area, 210 DEG C of 5th area, 210 DEG C of head) under squeezed out, the screw rod of extruder
Revolving speed 100r/min, control rate of feeding are no more than 5kg/h, and material carries out vacuum volatilization processing, extrudate before reaching head
Pelletizing, drying for standby after cooling.
(2) DSC is tested: carrying out DSC test to the granular samples that previous step is prepared.From room temperature with 50 DEG C/min's
Heating rate is heated at 220 DEG C after constant temperature 5min elimination thermal history, cools to 100 DEG C with the rate of 10 DEG C/min, constant temperature
5min is warming up to 220 DEG C from 100 DEG C with 10 DEG C/min again.Test data is shown in Table 1.
The spy of the polypropylene beta crystal nucleating agent being synthetically prepared to illustrate the invention concrete application in polypropylene material
Property, taking two kinds of widely used efficient polypropylene beta crystal nucleating agents respectively, (the terres rares nucleating agent 509 of commercialization reaches in Luoyang
Chemical industry；The amides nucleating agent TMB of commercialization, the production of Shanxi chemical institute) it compares, the corresponding nucleation agent content of comparative example
It is all 1000ppm, respectively comparative example 1 and comparative example 2.
The crystallization temperature data of each test specimens of table 1
As it can be seen from table 1 the crystallization temperature and beta crystal content of the obtained modified polypropene of the nucleating agent of different content are
It is distinguishing, when being nucleated agent content is 1000ppm, beta crystal content and crystallization temperature highest in sample, with nucleation agent content
It continues growing, the crystallization temperature of sample can gradually decrease, when nucleating agent additive amount of the present invention is greater than 800ppm, in gained sample
Beta crystal content is greater than or equal to comparative example beta crystal content, it can thus be appreciated that nucleating agent prepared by the present invention is a kind of excellent sub- amides
Beta crystal-type nucleater.
Beta crystal-type nucleater of the invention is applicable not only to acrylic resin, applies also for the polymerization of other imperfect crystals
In objects system, various applications are all belonged to the scope of protection of the present invention.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding changes and modifications, but these corresponding changes and modifications can be made according to the present invention by knowing those skilled in the art
It all should belong to the protection scope of the claims in the present invention.
Claims (5)
1. a kind of preparation method of Asia amides beta crystal-type nucleater, which is characterized in that this method comprises the following steps:
Melamine is added to the water by step 1, and acylating reagent and catalyst is then added, after 0.5~5h is stirred at room temperature, heating
To 80~160 DEG C reaction 10~for 24 hours, wherein the molar ratio of melamine, acylating reagent and catalyst be 1:1.05~1.3:0.1
~0.35；And
Step 2 cools to room temperature, and white precipitate is obtained by filtration, and washing is dried to obtain sub- amides beta crystal-type nucleater；
Wherein, the acylating reagent is mono-substituted phthalic anhydride, and wherein substituent group is the alkane of H, halogen or 1~10 carbon
Group composed by base；
The catalyst is triethylamine or to dimethylamino naphthyridine,
Shown in the structure such as formula (I) of the Asia amides beta crystal-type nucleater:
Wherein, R1, R2, R3, it is independent selected from H, halogen, 1~10 carbon alkyl.
2. the preparation method of Asia amides beta crystal-type nucleater according to claim 1, which is characterized in that described 1~10
The alkyl of carbon be methyl, ethyl, n-propyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, tert-butyl, n-pentyl, isopentyl,
N-hexyl or isohesyl.
3. the preparation method of Asia amides beta crystal-type nucleater according to claim 1, which is characterized in that the catalyst
For to dimethylamino naphthyridine.
4. the preparation method of Asia amides beta crystal-type nucleater according to claim 1, which is characterized in that the step 1
Heating temperature is 100~120 DEG C, and the reaction time is 10~14h.
5. application of the Asia amides beta crystal-type nucleater described in claim 1 in imperfect crystal polymer arts.
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| CN111925559B (en) * | 2019-05-13 | 2022-01-04 | 中国石油天然气股份有限公司 | Amide polyolefin beta-crystal form nucleating agent and preparation method and application thereof |
| CN114350062B (en) * | 2021-12-08 | 2023-05-02 | 界首市天鸿新材料股份有限公司 | High-rigidity low-yield polypropylene torsion film and preparation method thereof |
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