CN105061404B - A kind of sub- amide-type polypropylene beta crystal nucleating agent and preparation method thereof - Google Patents
A kind of sub- amide-type polypropylene beta crystal nucleating agent and preparation method thereof Download PDFInfo
- Publication number
- CN105061404B CN105061404B CN201510431147.0A CN201510431147A CN105061404B CN 105061404 B CN105061404 B CN 105061404B CN 201510431147 A CN201510431147 A CN 201510431147A CN 105061404 B CN105061404 B CN 105061404B
- Authority
- CN
- China
- Prior art keywords
- beta crystal
- compound
- hydroxyl
- halogen
- alkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 0 CC(*(CO)=O)N Chemical compound CC(*(CO)=O)N 0.000 description 3
Classifications
-
- 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
- C07D403/02—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 two hetero rings
- C07D403/06—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 two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- 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
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
- C08K5/3417—Five-membered rings condensed with carbocyclic rings
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of sub- amide-type polypropylene beta crystal nucleating agent, it has the general structure of Formulas I, wherein, n=0~20, R1For nitro, hydroxyl, amino, halogen or alkyl, R2One kind in following three kinds of groups：H, alkyl, contain carboxyl or hydroxyl or halogen or the group of heteroaromatic, R3One kind in following three kinds of groups：H, alkyl, contain carboxyl or hydroxyl or halogen or the group of heteroaromatic.The invention also discloses the preparation method of sub- amide-type polypropylene beta crystal nucleating agent.The present invention sub- amide-type polypropylene beta crystal nucleating agent have efficiently, be easily dispersed, it is green non-poisonous the characteristics of, beta crystal content reaches 81%, and decomposition temperature is higher, it will not be decomposed in the case of polypropylene is normally heated, dispersion effect is preferable, when addition is relatively low, degree is improved to polyacrylic performance apparent.
Description
Technical field
The present invention relates to a kind of polypropylene beta crystal nucleating agent and preparation method thereof, more particularly to a kind of sub- acid amides birdss of the same feather flock together third
Alkene beta crystal-type nucleater and preparation method thereof.
Background technology
Polyacrylic beta crystal is a kind of metastable-state crystal, belongs to hexagonal crystal system, under specific condition (as shearing, pressure or
Person adds nucleator) it could generate, with preferable toughness and shock resistance.
Find that gamma-quinacridinelone has β nucleation to polypropylene first from nineteen sixties Leugering H J.
Since effect, researchers increasingly pay close attention to the research and development of beta crystal-type nucleater and the research of mechanism.1981, Chinese Academy of Sciences Shanghai had
Machine history see first-class disclosed in the patents such as DE-A-3610644, CN1004076B, EP0682066 some dicarboxylic acids and
The compound of some of the main group of periodic table second metal oxide, hydroxide or salt composition, in common processing conditions just
Polypropylene can be induced to generate the higher beta crystal of content.The bright woods in Guangdong is taken in the fresh material Science and Technology Co., Ltd. and Chinese science
Institute's Guangzhou chemistry institute has developed a kind of mixed matching rare earth beta crystal-type nucleater WBG cooperatively, and is published in Chinese patent
In ZL00117339, when adding 0.15% WBG, beta crystal content reaches more than 90% in polypropylene, and not only nucleation efficiencies are high,
And color and luster is in bright milky, there is obvious advantage in terms of stability, nucleation selectivity.The Lv Zhiping of Institutes Of Technology Of Taiyuan
Deng a kind of dicarboxylate polypropylene beta crystal nucleating agent is disclosed in Chinese patent CN101418084A, the nucleator can have
The formation of effect ground induction polypropylene beta crystal.In addition, disclosing tetrahydrophthalic acid barium in Chinese patent CN102181092A
(PA4-Ba), carboxylic acid metal's salt compound of the THPA such as tetrahydrophthalic acid calcium is used as polypropylene beta crystal nucleating agent.Nothing
Machine class nucleator it is cheap, but nucleation efficiencies are relatively low, therefore can limit its application in high performance material.For
Condensed-nuclei aromatics complex structure, nucleation performance is good, but the coloring of product is deeper, so as to have impact on its scope used.Above-mentioned
The performance that beta crystal-type nucleater is improved by adding adjuvant is had no in these patents, is solved with beta crystal-type nucleater addition
Increase and cause the enlightenment for the problem of yield strength and bending modulus decline.
The common method of nucleator is added in industrial production synthetic method in melt blending and kettle.Comparatively, melt altogether
Mixing method technics comparing is simple, is generally used at present, the complexity that method synthesis technique compares in kettle, and being unfavorable for actual production should
With.
Either from practical application, environment-protecting and non-poisonous, or from the aspect of the academic research of mechanism of nucleation, new β is developed
Crystal-type nucleater is all necessary.
The content of the invention
It is an object of the invention to provide a kind of sub- amide-type polypropylene beta crystal nucleating agent of high-efficiency environment friendly.
It is a further object of the present invention to provide the preparation method of the polypropylene beta crystal nucleating agent.
To reach above-mentioned purpose, the present invention uses following technical scheme：
A kind of sub- amide-type polypropylene beta crystal nucleating agent, it has the general structure of Formulas I：
Wherein, n=0~20, R1For nitro, hydroxyl, amino, halogen or alkyl, R2One in following three kinds of groups
Kind：H, alkyl, contain carboxyl or hydroxyl or halogen or the group of heteroaromatic, R3One kind in following three kinds of groups：H, alkane
Base, contain carboxyl or hydroxyl or halogen or the group of heteroaromatic.
Further, R2For H, PhCH2-, the alkyl of 1~4 carbon atom, carboxyl, hydroxyl, halogen,OrR3For H, PhCH2-, the alkyl of 1~4 carbon atom, carboxyl, hydroxyl, halogen,Or
Further, n=0~4, R1For nitro, hydroxyl or amino, R2For H, CH3-、PhCH2-、OrR3For H, CH3-、PhCH2-、Or
Further, the sub- amide-type polypropylene beta crystal nucleating agent is one kind in the compound of following structural formula：
Compound I preparation method, using compound ii, compound III and compounds Ⅳ as raw material, temperature is -10~350
DEG C, compound I is made in reaction,
Wherein, n=0~20, R1For nitro, hydroxyl, amino, halogen or alkyl, R2One in following three kinds of groups
Kind：H, alkyl, contain carboxyl or hydroxyl or halogen or the group of heteroaromatic, R3One kind in following three kinds of groups：H, alkane
Base, contain carboxyl or hydroxyl or halogen or the group of heteroaromatic.
Further, the temperature is -10~250 DEG C.
Further, compound I preparation method is：By compound ii after 50~250 DEG C melt, ethylenediamine is added
And compound III, recrystallize after stirring reaction, then ethyl acetate is added thereto, it is placed in -10~10 DEG C of ice-water baths, adds three
Ethamine, and isobutyl chlorocarbonate is added, addition is cooled to -10~10 DEG C of compounds Ⅳ and sodium hydrate aqueous solution after reaction,
The stirring reaction under the conditions of ice-water bath, then ice-water bath is removed, room temperature reaction terminates rear stratification, water layer concentrated hydrochloric acid or second
Acid acidifying, separates out solid and is recrystallized with ethanol-water solution or directly use water filtration, obtain compound I.
In the present invention, the product of above-mentioned reaction is directly used after being separated with water filtration, now, it is possible some
The raw material not reacted completely is included wherein, but this performance impact to nucleator is little.
The sub- amide-type polypropylene beta crystal nucleating agent of the present invention can be scattered in high score with conventional high molecular processing method
In subbase body, be such as made master batch add matrix, be directly added into matrix, polymerization before added together with catalyst, or after polymerisation
Added before extruding pelletization etc..When in use, no matter the beta crystal-type nucleater is to be directly added into or be added with master batch, and it is in matrix
Final consumption in acrylic resin is between 0.00001~50% (weight ratio), preferably 0.0001~20%.
The invention has the advantages that：
1 the present invention sub- amide-type polypropylene beta crystal nucleating agent have efficiently, be easily dispersed, it is green non-poisonous the characteristics of,
When addition is 0.05~0.6wt% in polypropylene, polyacrylic crystallization temperature, crystallinity can be effectively improved, is significantly improved
Polyacrylic impact strength, heat distortion temperature etc.；Tested, be computed by DSC, beta crystal content reaches 81%.
The decomposition temperature of the sub- amide-type nucleator of 2 present invention is higher, will not be decomposed in the case of polypropylene is normally heated,
And dispersion effect is preferably, when addition is relatively low, degree is improved to polyacrylic performance apparent.
The preparation method of the sub- amide-type nucleator of 3 present invention, synthesis step is simple, and solvent used is more environmentally friendly, right
The harm of environment is small, and cost of material is relatively low.
Brief description of the drawings
Fig. 1 is the melting curve of second of temperature-rise period of the DSC tests of the embodiment of the present invention 15；
Fig. 2 is the crystallization process curve of the DSC tests of the embodiment of the present invention 15.
Embodiment
With reference to specific embodiment, the present invention is described further：
Embodiment 1
After the commercially available phthalic anhydride meltings of 0.06mol, 2mL ethylenediamines are added, 0.05mol alpha-amido is added
Recrystallized after β-imidazole radicals propionic acid, stirring reaction 4h, then add 120mL ethyl acetate thereto, flask is placed in -10~10 DEG C
In ice-water bath, 0.15mL triethylamines are added, and are slowly added to after 20.0g isobutyl chlorocarbonates, reaction 2h, 0.15mol have been added
Through being cooled to -10~10 DEG C of amion acetic acid and 20mL sodium hydrate aqueous solutions in advance, when stirring one section under the conditions of ice-water bath
Between after, then remove ice-water bath, react at room temperature 2h, reaction solution stratification, water layer is acidified with concentrated hydrochloric acid, separate out solid with ethanol-
The aqueous solution is recrystallized, and obtains the sub- amide-type polypropylene beta crystal nucleating agent of following structural formula：
Embodiment 2
After the commercially available phthalic anhydride meltings of 0.06mol, 2mL ethylenediamines are added, 0.05mol amino second is added
Recrystallized after acid, stirring reaction 8h, then add 120mL ethyl acetate thereto, flask is placed in -10~10 DEG C of ice-water baths,
0.15mL triethylamines are added, and are slowly added to after 20.0g isobutyl chlorocarbonates, reaction 10h, 0.15mol are added cold in advance
But to -10~10 DEG C of amion acetic acid and 180mL sodium hydrate aqueous solutions, after stirring a period of time under the conditions of ice-water bath, then
Ice-water bath is removed, 24h is reacted at room temperature, reaction solution stratification, water layer acetic acid separates out solid and directly uses water filtration, obtains
To the sub- amide-type polypropylene beta crystal nucleating agent of following structural formula：
Embodiment 3
After the commercially available phthalic anhydride meltings of 0.06mol, 2mL ethylenediamines are added, 0.05mol phenylpropyl alcohol ammonia is added
Recrystallized after acid, stirring reaction 6h, then add 120mL ethyl acetate thereto, flask is placed in -10~10 DEG C of ice-water baths,
0.15mL triethylamines are added, and are slowly added to after 20.0g isobutyl chlorocarbonates, reaction 5h, 0.15mol is added and cools down in advance
To -10~10 DEG C of amion acetic acid and 100mL sodium hydrate aqueous solutions, after stirring a period of time under the conditions of ice-water bath, then remove
Ice-water bath is removed, 10h is reacted at room temperature, reaction solution stratification, water layer is acidified with concentrated hydrochloric acid, solid ethanol-water solution weight is separated out
Crystallization, obtains the sub- amide-type polypropylene beta crystal nucleating agent of following structural formula：
Describe for convenience below, be designated as product WBH.
Embodiment 4
After 0.06mol 3- hydroxyl phthalic anhydrides are melted, add 2mL ethylenediamines, add 0.05mol α-
Recrystallized after amino β-imidazole radicals propionic acid, stirring reaction 6h, then add 120mL ethyl acetate thereto, flask is placed in -10~
In 10 DEG C of ice-water baths, 0.15mL triethylamines are added, and are slowly added to after 20.0g isobutyl chlorocarbonates, reaction 8h, are added
0.15mol has been cooled to -10~10 DEG C of alpha-amido β-imidazole radicals propionic acid and 120mL sodium hydrate aqueous solutions in advance, in ice
Stirred under water bath condition after a period of time, then remove ice-water bath, react at room temperature 12h, reaction solution stratification, water layer acetic acid acid
Change, separate out solid and directly use water filtration, obtain the sub- amide-type polypropylene beta crystal nucleating agent of following structural formula：
Embodiment 5
After 0.06mol 3- aminophthalic acids acid anhydride is melted, 2mL ethylenediamines are added, 0.05mol benzene is added
Recrystallized after alanine, stirring reaction 6h, then add 120mL ethyl acetate thereto, flask is placed in -10~10 DEG C of ice-water baths
In, 0.15mL triethylamines are added, and be slowly added to after 20.0g isobutyl chlorocarbonates, reaction 4h, add 0.15mol prior
- 10~10 DEG C of phenylalanine and 50mL sodium hydrate aqueous solutions are cooled to, after stirring a period of time under the conditions of ice-water bath, then
Ice-water bath is removed, 6h is reacted at room temperature, reaction solution stratification, water layer is acidified with concentrated hydrochloric acid, solid ethanol-water solution weight is separated out
Crystallization, obtains the sub- amide-type polypropylene beta crystal nucleating agent of following structural formula：
Embodiment 6
By polypropylene (trade mark F401, melt body flow rate 2.5g/10min, density 0.91g/cm of 100 parts by weight3) use
Two-roll mill is kneaded under the conditions of 180 DEG C, and 0.5 parts by weight beta crystal-type nucleater WBH of embodiment 3, mixing are added after plasticizing
Bottom sheet after 3min, is then molded into the thick sheet materials of 1mm in 200 DEG C with vulcanizing press, is designated as PP-WBH-1.
Using Perkin-Elmer differential scanning calorimeters (DSC), in N2Under protection, it is heated to 10 DEG C/min speed
210 DEG C, constant temperature 5min to eliminate thermal history, then with 10 DEG C/min speed is cooled to 30 DEG C, then be heated to 210 with 10 DEG C/min
DEG C, record second of melting process of sample.As a result, the brilliant melting peak T of β are occurred in that near 154 DEG C1, heat content is △ Hβ, 168
The brilliant melting peak T of α are occurred in that near DEG C2, heat content is △ Hα, the relative amount of beta crystal is by following formula (1) calculating：
kβ=△ Hβ/(△Hα+△Hβ) × 100% (1)
It can also be tried to achieve by Wide angle X-ray diffraction (WAXD) using following Turner-Jones formula (2)：
kx=H (300)/[H (300)+H (110)+H (040)+H (130)] × 100% (2)
H (300) is the diffraction peak heights of beta crystal in formula, and H (110), H (040), H (130) are the height of alpha-crystal form diffraction maximum
Degree.
Pure polypropylene (trade mark is F401) can also make batten as stated above, PP-0 is designated as, also according to above-mentioned side
Method is tested.Correlated results is as shown in table 1.
The polypropylene crystal formation content balance and crystallization temperature of the virgin pp of table 1 and addition beta crystal-type nucleater
As shown in Table 1, added in polypropylene the present invention beta crystal-type nucleater after, beta crystal content reach 70.5% or
81%.
Embodiment 7
The polypropylene (trade mark PP F401) of 100 parts by weight is kneaded with two-roll mill under the conditions of 180~185 DEG C, moulded
After change add embodiment 3 0.25 parts by weight beta crystal-type nucleater WBH, mixing 5min after bottom sheet, then with vulcanizing press in
200 DEG C, 10MPa is molded into the thick sheet materials of 4mm, is designated as PP-WBH-2, the dumbbell shape of standard is then fabricated on sampling machine
(pressing GB GB/T1040-92) and rectangular specimen (pressing GB/T1043-1993), impact batten is in breach sample preparation by rectangle batten
Breach (pressing GB/1843-1996) is made on machine.Meanwhile, pure polypropylene (trade mark is F401) can also make as stated above
Batten, then after 23 DEG C of constant temperature 24h, carries out Mechanics Performance Testing, heat distortion temperature test, the data obtained is as shown in table 2.
Table 2
As shown in Table 2, added in polypropylene the present invention beta crystal-type nucleater after, the impact strength of resulting materials and
Heat distortion temperature is improved.
Embodiment 8
The 0.3 parts by weight beta crystal-type nucleater of addition embodiment 3 in the polypropylene (trade mark PP F401) of 100 parts by weight
Used after WBH, mixing and Mechanics Performance Testing, heat are carried out after injection moulding after double screw extruder extruding pelletization, cooling, constant temperature 24h
Deformation temperature is tested, and is designated as PP-WBH-3, meanwhile, pure polypropylene (trade mark is F401) can also make sample as stated above
Bar, then after 23 DEG C of constant temperature 24h, carries out Mechanics Performance Testing, heat distortion temperature test, the data obtained is as shown in table 3.
Table 3
As shown in Table 3, added in polypropylene the present invention beta crystal-type nucleater after, the impact strength of resulting materials and
Heat distortion temperature is improved.
Embodiment 9
The 0.1 parts by weight beta crystal-type nucleater of addition embodiment 3 in the polypropylene (trade mark PPH-T03) of 100 parts by weight
Injection moulding after double screw extruder extruding pelletization, cooling is used after WBH, mixing, PP-WBH-4 is designated as, meanwhile, pure polypropylene
(trade mark is PPH-T03) can also make batten as stated above, then carry out power after constant temperature 24h after 23 DEG C of constant temperature 24h
Performance test, heat distortion temperature test are learned, the data obtained is as shown in table 4.
Table 4
As shown in Table 4, added in polypropylene the present invention beta crystal-type nucleater after, the impact strength of resulting materials and
Heat distortion temperature is improved.
Embodiment 10
0.15 part of beta crystal-type nucleater WBH of addition embodiment 3 in the polypropylene (trade mark PPH-T03) of 100 parts by weight,
Injection moulding after double screw extruder extruding pelletization, cooling is used after mixing, PP-WBH-5 is designated as, meanwhile, the pure polypropylene (trade mark
For PPH-T03) batten can also be made as stated above, Mechanics Performance Testing, heat distortion temperature are then carried out after equal constant temperature 24h
Test, the data obtained is as shown in table 5.
Table 5
As shown in Table 5, added in polypropylene the present invention beta crystal-type nucleater after, the impact strength of resulting materials and
Heat distortion temperature is improved.
Embodiment 11
The 1 parts by weight beta crystal-type nucleater WBH of addition embodiment 3 in the polypropylene (trade mark PPH-T03) of 100 parts by weight,
Double screw extruder extruding pelletization is used after mixing, master batch is obtained, 90 parts of virgin pps then will be taken to be well mixed with 10 parts of master batches
Afterwards, after being extruded with rheometer, cooling is broken, and injection moulding is designated as PP-WBH-6, meanwhile, (trade mark is PPH- to pure polypropylene
T03 batten) can also be made as stated above, and Mechanics Performance Testing, heat distortion temperature test are then carried out after equal constant temperature 24h,
The data obtained is as shown in table 6.
Table 6
As shown in Table 6, added in polypropylene the present invention beta crystal-type nucleater after, the impact strength of resulting materials and
Heat distortion temperature is improved.
Embodiment 12
The polypropylene (trade mark F401) of 100 parts by weight is kneaded into plasticizing with two-roll mill under the conditions of 180~185 DEG C
Afterwards, after the beta crystal-type nucleater WBH and 0.05 part of rare earth nucleator WBG-II of 0.05 parts by weight of addition embodiment 3, mixing 5min
Bottom sheet, is then molded into the thick sheet materials of 4mm in 200 DEG C, 10MPa with vulcanizing press, PP-WBH-7 is designated as, then in sampling machine
On be fabricated to the dumbbell shape (by GB GB/T1040-92) and rectangular specimen (by GB/T1043-1993) of standard, by rectangle batten
Breach (pressing GB/1843-1996) is made on breach sampling machine.Meanwhile, pure polypropylene (trade mark is F401) can also be by upper
State method and make batten, then after 23 DEG C of constant temperature 24h, carry out Mechanics Performance Testing, heat distortion temperature test, the data obtained
As shown in table 7.
Table 7
As shown in Table 7, added in polypropylene the present invention beta crystal-type nucleater after, the impact strength of resulting materials and
Heat distortion temperature is improved.
Embodiment 13
The 0.15 parts by weight beta crystal-type nucleater of addition embodiment 3 in the polypropylene (trade mark PP F401) of 100 parts by weight
WBH and 0.1 parts by weight beta crystal-type nucleater TMB-5 (Shanxi-Prov Inst of Chemical Industry), is extruded after being well mixed with double screw extruder
Granulation, injection moulding after cooling is designated as PP-WBH-8, meanwhile, pure polypropylene (trade mark is F401) can also be as stated above
Batten is made, Mechanics Performance Testing, heat distortion temperature test are then carried out after equal constant temperature 24h, the data obtained is as shown in table 8.
Table 8
As shown in Table 8, added in polypropylene the present invention beta crystal-type nucleater after, the impact strength of resulting materials and
Heat distortion temperature is improved.
Embodiment 14
The 0.05 parts by weight beta crystal-type nucleater of addition embodiment 3 in the polypropylene (trade mark PP F401) of 100 parts by weight
WBH, 0.05 parts by weight rare earth nucleator WBG-II and 0.05 parts by weight beta crystal-type nucleater TMB-5 (Shanxi-Prov Inst of Chemical Industry),
After well mixed, the processing aids such as antioxidant, lubricant are added, double screw extruder extruding pelletization is used after being well mixed again,
Injection moulding after cooling, is designated as PP-WBH-10, meanwhile, pure polypropylene (trade mark is F401) can also make as stated above
Batten, then carries out Mechanics Performance Testing, heat distortion temperature test after equal constant temperature 24h, the data obtained is as shown in table 9.
Table 9
As shown in Table 9, added in polypropylene the present invention beta crystal-type nucleater after, the impact strength of resulting materials and
Heat distortion temperature is improved.
Embodiment 15
0.1 part of beta crystal-type nucleater WBH of addition in the polypropylene (trade mark PPH-T03) of 100 parts by weight, after being well mixed,
The processing aids such as antioxidant, lubricant are added, are molded into after using double screw extruder extruding pelletization, cooling after being well mixed again
Type.A fritter is taken to carry out DSC tests in the batten of injection, as a result as shown in Figure 1 and Figure 2, Fig. 1 is second liter of DSC tests
The melting curve of warm process, Fig. 2 is the crystallization process curve of DSC tests；The polypropylene for adding beta crystal-type nucleater is curve 1,3,
Pure polypropylene is curve 2,4；It is about 81% to be computed beta crystal content.
The foregoing is only a specific embodiment of the invention, but protection scope of the present invention is not limited thereto, any
Belong to those skilled in the art the invention discloses technical scope in, the change or replacement that can be readily occurred in, all should
It is included within the scope of the present invention.Therefore, protection scope of the present invention should be defined by scope of the claims.
Claims (6)
1. a kind of sub- amide-type polypropylene beta crystal nucleating agent, it is characterised in that it has the general structure of Formulas I, or is chemical combination
Thing 1, compound 2：
Wherein, n=0~20 and n are not 0, R1For nitro, hydroxyl, amino, halogen or alkyl, R2For H, PhCH2-, 1~4 carbon
The alkyl of atom, carboxyl, hydroxyl, halogen,R3For H, PhCH2-, the alkyl of 1~4 carbon atom,
Carboxyl, hydroxyl, halogen,
2. sub- amide-type polypropylene beta crystal nucleating agent according to claim 1, it is characterised in that n=0~4 and n is not
0, R1For nitro, hydroxyl or amino, R2For H, CH3-、PhCH2-、R3For H, CH3-、PhCH2-、
3. sub- amide-type polypropylene beta crystal nucleating agent according to claim 1, it is characterised in that it is following structural formula
Compound in one kind：
4. compound I preparation method, it is characterised in that using compound ii, compound III and compounds Ⅳ as raw material, temperature
For -10~350 DEG C, compound I is made in reaction,
Wherein, n=0~20 and n are not 0, R1For nitro, hydroxyl, amino, halogen or alkyl, R2For H, PhCH2-, 1~4 carbon
The alkyl of atom, carboxyl, hydroxyl, halogen,R3For H, PhCH2-, the alkyl of 1~4 carbon atom,
Carboxyl, hydroxyl, halogen,
5. compound I according to claim 4 preparation method, it is characterised in that the temperature is -10~250 DEG C.
6. compound I according to claim 4 preparation method, it is characterised in that after compound ii is melted, is added
Recrystallized after ethylenediamine and compound III, stirring reaction, then add ethyl acetate thereto, be placed in -10~10 DEG C of ice-water baths,
Triethylamine is added, and adds isobutyl chlorocarbonate, addition is cooled to -10~10 DEG C of compounds Ⅳ and NaOH water after reaction
Solution, the stirring reaction under the conditions of ice-water bath, then ice-water bath is removed, room temperature reaction terminates rear stratification, water layer concentrated hydrochloric acid
Or acetic acid, separate out solid and recrystallized with ethanol-water solution or directly use water filtration, obtain compound I.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510431147.0A CN105061404B (en) | 2015-07-21 | 2015-07-21 | A kind of sub- amide-type polypropylene beta crystal nucleating agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510431147.0A CN105061404B (en) | 2015-07-21 | 2015-07-21 | A kind of sub- amide-type polypropylene beta crystal nucleating agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105061404A CN105061404A (en) | 2015-11-18 |
| CN105061404B true CN105061404B (en) | 2017-07-11 |
Family
ID=54490968
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510431147.0A Active CN105061404B (en) | 2015-07-21 | 2015-07-21 | A kind of sub- amide-type polypropylene beta crystal nucleating agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105061404B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109054171B (en) * | 2018-06-28 | 2021-09-14 | 广东炜林纳新材料科技股份有限公司 | Polypropylene toughening nucleating agent and preparation method thereof |
| CN109535557A (en) * | 2018-11-26 | 2019-03-29 | 铜陵熙成塑料制品有限公司 | A kind of high-ductility plastic packaging bag material |
| CN113292787B (en) * | 2021-05-08 | 2022-04-08 | 华南理工大学 | Beta crystal form nucleating agent and preparation method and application thereof |
| CN114085425B (en) * | 2021-11-08 | 2023-03-28 | 宁波福天新材料科技有限公司 | Beta-crystal-form compound nucleating agent and application thereof |
| CN116496202B (en) * | 2023-05-06 | 2024-03-01 | 安徽工业大学 | Fluorescent probe for diethyl chlorophosphate detection and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2656620A1 (en) * | 1990-01-04 | 1991-07-05 | M & T Chemicals Inc | Synthetic polyolefin resin composition containing a nucleating agent |
| CN101343313A (en) * | 2008-09-03 | 2009-01-14 | 南京农业大学 | Glucose dipeptide compounds, preparation method and application thereof |
| CN103889972A (en) * | 2011-10-21 | 2014-06-25 | 奇斯药制品公司 | Derivatives of 1-phenyl-2-pyridinyl alkyl alcohols as phosphodiesterase inhibitors |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10137163A1 (en) * | 2001-07-30 | 2003-02-13 | Bayer Ag | New thiophenecarboxamido-substituted isoindole derivatives, useful as Factor XIa inhibitors for treatment or prophylaxis of, e.g. thromboembolic diseases, atherosclerosis, arthritis, Alzheimer's disease or cancer |
| AU2003297904A1 (en) * | 2003-12-12 | 2005-07-14 | University Of Maryland, Baltimore | Immunomodulatory compounds that target and inhibit the py+3 binding site of tyrosene kinase p56 lck sh2 domain |
-
2015
- 2015-07-21 CN CN201510431147.0A patent/CN105061404B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2656620A1 (en) * | 1990-01-04 | 1991-07-05 | M & T Chemicals Inc | Synthetic polyolefin resin composition containing a nucleating agent |
| CN101343313A (en) * | 2008-09-03 | 2009-01-14 | 南京农业大学 | Glucose dipeptide compounds, preparation method and application thereof |
| CN103889972A (en) * | 2011-10-21 | 2014-06-25 | 奇斯药制品公司 | Derivatives of 1-phenyl-2-pyridinyl alkyl alcohols as phosphodiesterase inhibitors |
Non-Patent Citations (3)
| Title |
|---|
| CAS号874531-35-8;STN-REGISTRY;《STN-REGISTRY数据库》;20060217 * |
| Cyclic imides. III. Derivatives of l(2H)-isoquinolone.2. A study of the hydroxy- and methoxyphthalimidoacetic acids and the methyl methoxyphthalimidoacetates;Caswell, Lyman R.等;《Journal of Heterocyclic Chemistry》;19661231;第3卷(第3期);第328-332页 * |
| Nitrophthaloyl and aminophthaloyl derivatives of amino acids;Caswell, Lyman R.等;《Journal of Chemical and Engineering Data》;19681231;第13卷(第2期);第291-292页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105061404A (en) | 2015-11-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105061404B (en) | A kind of sub- amide-type polypropylene beta crystal nucleating agent and preparation method thereof | |
| TWI461472B (en) | Β-nucleating agent composite for polypropylene and the use of the same | |
| CN104004304B (en) | PVC material with shape memory function | |
| JP2010514846A (en) | β-nucleating agent and method for producing the same | |
| CN113621175B (en) | Efficient isotactic polypropylene beta-crystal form nucleating agent and preparation method and application thereof | |
| CN104212034A (en) | Carrier-free plastic master batch and preparation method and application of carrier-free plastic master batch | |
| CN106810714A (en) | A kind of nucleating agent compositions and its application | |
| CN114989586A (en) | Polyhydroxyalkanoate composition containing alcohol nucleating agent, polyhydroxyalkanoate molded body and preparation method thereof | |
| CN114989583A (en) | Acid nucleating agent for polyhydroxyalkanoate and polyhydroxyalkanoate molded body | |
| WO2024045338A1 (en) | Granulation processing method for degradable material and formed body prepared thereby | |
| CN104478692B (en) | A kind of synthetic method of multi-hydroxy stearic acid salt | |
| CN115232456A (en) | Polyhydroxyalkanoate composition containing hydroxy acid nucleating agent, polyhydroxyalkanoate molded body and preparation method thereof | |
| CN106866636B (en) | Imide β crystal form nucleating agent, and preparation method and application thereof | |
| Ren et al. | Nucleation effect of adipic acid metal salts in isotactic polypropylene | |
| CN115232455B (en) | Polyhydroxyalkanoate composition containing ester nucleating agent, polyhydroxyalkanoate molded body and preparation method thereof | |
| CN108504068A (en) | A kind of high endurance fire retardation PC/PBT alloy material and preparation method thereof | |
| CN115890962B (en) | Granulation processing method of low-melt-index degradable material and formed body prepared by same | |
| CN104629354B (en) | Nucleation lubricant for nylon and preparation method of nucleation lubricant | |
| CN107474495B (en) | Modified PBAT resin composition and preparation method thereof | |
| CN106810715A (en) | A kind of nucleating agent compositions and its application | |
| CN104877172A (en) | Method for modifying fast-crystallization high-crystallinity polylactic acid | |
| CN113861058A (en) | Triamido methylbenzene nucleating agent, preparation method and use method | |
| CN106831627B (en) | Amide β crystal form nucleating agent, and preparation method and application thereof | |
| CN102167710B (en) | Preparation method of organic phosphate type polypropylene transparent nucleating agent | |
| CN106084465A (en) | A kind of terres rares polypropylene reinforcement nucleating agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |