CN104420001A - Monofilament based on polyamide composition - Google Patents
Monofilament based on polyamide composition Download PDFInfo
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- CN104420001A CN104420001A CN201310399020.6A CN201310399020A CN104420001A CN 104420001 A CN104420001 A CN 104420001A CN 201310399020 A CN201310399020 A CN 201310399020A CN 104420001 A CN104420001 A CN 104420001A
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- polyamide
- monofilament
- weight
- carbon atom
- daiamid composition
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Abstract
The invention relates to a monofilament based on polyamide composition which comprises at least 70wt% of polyamides condensed from the following matters: aliphatic diamine comprising 4-18 carbon atoms, aliphatic (alicyclic) diacid comprising 10-18 carbon atoms and aliphatic monocarboxylic acid which is used as a chain terminator and comprises 2-12 carbon atoms. The invention further relates to a method for preparing the monofilament.
Description
Technical field
The present invention relates to based on daiamid composition monofilament and prepare its method.
Background technology
Polymer filament such as polyamide monofilament is widely used in toothbrush and other brush-type family expenses and industrial article.
Polyamide 6 .12 and polyamide 6 .10 is two kinds of modal examples for the polymer in such application.
Polyamide monofilament uses extrusion method manufacture.At industrial scale, extrusion method carries out at high speeds and with long time-quantum method.In these cases, along with the stability (particularly processing stability and color stability) of time and at high temperature both polymeric articles is crucial.
Therefore, there is the demand that the monofilament prepared by the daiamid composition of the stability with improvement (particularly processing stability and color stability) is provided.
Summary of the invention
The first object of the present invention is to provide the monofilament prepared by daiamid composition, and described daiamid composition comprises the polyamide obtained by the condensation of following material of at least 70 % by weight:
-comprise the aliphatic diamine of 4-18 carbon atom, and
-comprise aliphatic (alicyclic) diacid of 10-18 carbon atom, and
-as the aliphatic monocarboxylic acid comprising 2-12 carbon atom of chain terminating agent.
According to an embodiment, described aliphatic monocarboxylic acid is acetic acid and/or laurate.
According to an embodiment, described aliphatic diamine comprises 5-12 carbon atom, preferably 6 carbon atoms.
According to an embodiment, described polyamide is:
-there is the polyamide 6 .10 of acetamide-end group; Or
-there is the polyamide 6 .10 of lauramide-end group; Or
-there is the polyamide 6 .12 of acetamide-end group; Or
-there is the polyamide 6 .12 of lauramide-end group.
According to an embodiment, described daiamid composition comprises the described polyamide of at least 75 % by weight, preferably at least 80 % by weight or at least 85 % by weight or at least 90 % by weight or at least 95 % by weight or at least 98 % by weight or at least 99 % by weight.
According to an embodiment, described daiamid composition also comprises one or more fluorescent whitening agents and/or one or more antioxidants except described polyamide, preferably adds that described polyamide forms by one or more fluorescent whitening agents and/or one or more antioxidants.
Another object of the present invention is to provide the method preparing monofilament, comprises and daiamid composition is extruded through die head, and wherein said daiamid composition comprises the polyamide obtained by the condensation of following material of at least 70 % by weight:
-comprise the aliphatic diamine of 4-18 carbon atom, and
-comprise aliphatic (alicyclic) diacid of 10-18 carbon atom, and
-as the aliphatic monocarboxylic acid comprising 2-12 carbon atom of chain terminating agent.
According to an embodiment, described aliphatic monocarboxylic acid is acetic acid and/or laurate.
According to an embodiment, described daiamid composition is as above.
Another object of the present invention is to provide the aliphatic monocarboxylic acid that comprises 2-12 carbon atom as the purposes of chain terminating agent for the stable monofilament prepared by daiamid composition, and described daiamid composition comprises the polyamide obtained by the condensation of following material of at least 70 % by weight:
-comprise the aliphatic diamine of 4-18 carbon atom, and
-comprise aliphatic (alicyclic) diacid of 10-18 carbon atom.
According to an embodiment, described aliphatic monocarboxylic acid is acetic acid and/or laurate.
According to an embodiment, described daiamid composition is as above.
Another object of the present invention is to provide the amenities comprising one or more above-mentioned monofilament, and described amenities is preferably toothbrush.
Another object of the present invention is to provide the cleaning supplies comprising one or more above-mentioned monofilament, and described cleaning supplies are preferably brush.
The invention enables the shortcoming that can overcome prior art.Especially, the monofilament that can provide and be prepared by daiamid composition is provided, it has the stability (processing stability particularly improved and/or the color stability of improvement) of improvement, keeps the required engineering properties-of monofilament simultaneously or even improves described engineering properties according to some embodiments.
This realizes as the chain terminating agent being used for polyamide by using laurate and/or acetic acid (or other comprises the aliphatic monocarboxylic acid of 2-12 carbon atom).
Have been found that the chain terminating agent of the type improves the stability of polyamide, keep the engineering properties of (or even improving) monofilament simultaneously.
And, have been found that the chain terminating agent of the type is better than trending towards causing other conventional chain terminating agent of less desirable side effect.
Such as, benzoic acid is conventional chain terminating agent, but it exists the processing temperature of needs rising and produces less desirable benzene genus (benzenic) compound.
Similarly, stearic acid is another kind of conventional chain terminating agent, but it exists the monofilament causing having the sliding sensation of fats/oils or sense of touch, makes them be inappropriate for great majority application.
Lauryl amine is another kind of possible chain terminating agent, but it causes the less desirable painted of product.
Detailed description of the invention
Present will in the following description in more detail and do not describe the present invention with limiting.
All ratios are percetages by weight, except as otherwise noted.
The present invention utilizes the daiamid composition of polyamide based on being marked as PA X.Y, and wherein X is the integer of 4-18 (preferred 5-12) and Y is the integer of 10-18 (preferred 10-12).
X and Y represents the respective residue of condensation coming from aliphatic diamine and aliphatic (alicyclic) diacid, preferred aliphat diacid.
Preferably, PA6.12 (nylon 612) or PA6.10 (polyhexamethylene sebacamide) is used.
In addition, the aliphatic monocarboxylic acid comprising 2-12 carbon atom is used as chain terminating agent in the polymerization process producing PA X.Y polyamide.
This chain terminating agent can be straight or branched, preferred straight chain.It can be replacement or unsubstituted, and preferably unsubstituted.
Acetic acid and/or laurate are ready to use in the preferred chain terminating agent in the polymerization process producing PA X.Y polyamide.Acetic acid is formula CH
3the acid of COOH.Laurate is formula C
11h
23the acid of COOH.
Other possible terminator comprises following linear monocarboxylic acid: C
2h
5cOOH; C
3h
7cOOH; C
4h
9cOOH; C
5h
11cOOH; C
6h
13cOOH; C
7h
15cOOH; C
8h
17cOOH; C
9h
19cOOH; And C
10h
21cOOH.
The amine end groups of described monocarboxylic acid and polyamide reacts to produce C2-C12 acid amides-end group, such as various-(NHCO-CH
3) and-(NHCO-C
11h
23) acetamide/lauramide-end group.
The term " polyamide of C2-C12 acid amides-end " used in this application refers to that at least part of independent (individual, individual) polyamide molecule has at least one such C2-C12 acid amides-end group (as acetamide and/or lauramide-end group).But should emphasize, this is statistical concept, and usually, some independent polyamide molecule do not have acid amides-end group, some independent polyamide molecule have an acid amides-end group (one end at polyamide chains), and some independent polyamide molecule have two acid amides-end groups (two ends at polyamide chains).
According to an embodiment, the only a kind of of above-mentioned monocarboxylic acid is used as chain terminating agent, such as only acetic acid or only laurate.
Alternatively, the mixture of two or more of above-mentioned monocarboxylic acid can be used as chain terminating agent (as acetic acid and laurate), and the PA X.Y polyamide obtained in this case comprises multiple acid amides-end group.
In addition, the mixture of two or more of the PA X.Y of above C2-C12 acid amides-end can be used: the mixture of the PA6.12 of such as lauramide or acetamide-end and the PA6.10 of lauramide or acetamide-end.
But, preferably use the PA X.Y polyamide of only a kind of such C2-C12 acid amides-end, the PA6.10 of such as only lauramide or acetamide-end, or the PA6.12 of only lauramide or acetamide-end.
The PA X.Y of described C2-C12 acid amides-end preferably has 10,000-40, the molecular weight of 000g/mol.
The PA X.Y of described C2-C12 acid amides-end such as can pass through melting-polymerization preparation.The mixture that first described polymer comprises monomer (diamines and diacid), water (make the stirring of medium easier), described chain terminating agent and optional additive (heat stabilizer, defoamer etc.) by heating at high temperature and pressure obtains.This step usually the temperature of 100-300 DEG C and 3-35 bar pressure under carry out.
Then by degassed removing steam and reduce pressure until reach atmospheric pressure.In third step process, polycondensation occurs under nitrogen purge or under vacuo, to reach required molecular weight.
The content of the chain terminating agent introduced calculates according to required molecular weight.Possible scope is 25-100mmol/kg polymer.
According to one preferred embodiment, described daiamid composition comprises the PA X.Y of above-mentioned C2-C12 acid amides-end as polyamide component unique in described composition.Alternatively, except those, also can comprise one or more other polyamide compounds (described other polyamide compound is used or prepared without chain terminating agent) in the composition.The part by weight of PA X.Y in (all) compositions of C2-C12 acid amides-end is at least 70%, preferably at least 75% or at least 80% or at least 85% or at least 90% or at least 95% or at least 98% or at least 99%.
If existed, described other polyamide such as can be selected from PA11 and PA12.Also copolyamide can be used.
The additive that other is possible can be there is, such as:
-fluorescent whitening agent (with relative to whole composition be less than 0.1% amount);
-antioxidant (with relative to whole composition be less than 1% amount);
Advantageously, the described daiamid composition used in the present invention is not containing any additive in addition to that mentioned above.Especially, advantageously, this daiamid composition is not containing any filler or reinforcing material.
Described daiamid composition by by the PA X.Y of C2-C12 acid amides-end and other optional component compounding and prepare.Described composition is collected with ball (sheet, pellet) or the form of particle usually.
By above-mentioned daiamid composition for the preparation of monofilament.Monofilament is the silk (yarn, yarn) be made up of the synthetic fiber that sub-thread is non-twist.
Described daiamid composition preferably provides with pellet form.Typically by it from hopper feed to the cylinder of extruder comprising rotary screw.This rotary screw forces particle in cylinder forward, and it is heated to required melt temperature (it can be as 250 DEG C-300 DEG C).
Advantageously can set and add heat distribution (profile) for cylinder, wherein some independently controlled heater districts make the temperature of cylinder from behind (material here enters) to raising gradually above.This allows described material be pushed through described cylinder along with it and melt gradually, and reduces the overheated risk that can cause the degraded in described polymer.
Alternatively, melt temperature is kept by friction independent in cylinder inside and pressure.If produce too many heat, cooling device can be provided.
Before described cylinder, the composition of melting leaves screw rod and can be advanced through net group (screen pack) to remove any pollutant in melt.Described net strengthens by filter offset plate (breaker plate).Described net group/filter offset plate assembly is also used in cylinder and produces back pressure.Molten homogeneous for composition can need back pressure with suitably mixing.The combination of filter offset plate and net group also can make described composition preformed on y direction.
Then, this melt composition enters die head, and this gives its profile to described monofilament.Then described monofilament can be cooled, such as, by being pulled through water-bath.
If there is additive, they can work as described compounding of polymers adds when being particle, or they can direct charging together with polyamide granules (form with liquid or ball) in extruder.
The monofilament obtained thus can have the diameter of 0.02mm-3mm, preferably 0.05-1.6mm.
Monofilament of the present invention can be used for manufacturing various brush and particularly toothbrush.Other application comprises grinding silk, synthesis brush silk, dental care silk, filter, machine clothing (paper machine clothing), painting brush and cosmetic product.
embodiment
The following example illustrates the present invention but does not limit the present invention.
embodiment 1: polymerization process
Under agitation introduce following component in the reactor:
-23.26kg dodecanedioic acid;
-11.73kg hexamethylene diamine;
-157.63g acetic acid;
-2kg water; With
-1.32g defoamer (silicone oil).
Under agitation reactor heating, until internal temperature reaches 240 DEG C, removes the water of formation to maintain the internal pressure of 14 bar simultaneously gradually.
The internal pressure of reactor was reduced to atmospheric pressure 1 hour period and carries out nitrogen wash subsequently until reach required viscosity.
embodiment 2 – stability
Assess the viscosity stability according to embodiment 1 or similar to Example 1 the four kinds of polyamide compounds prepared and color stability, i.e. standard P the A6.12 (=not PA6.12 for preparing of usage chain terminator), standard P the A6.10 (=not PA6.10 for preparing of usage chain terminator), the PA6.12 (PA6.12 prepared by=usage chain terminator) of preparation and the PA6.10 (PA6.10 prepared by=usage chain terminator) of preparation.
Viscosity stability is assessed by monitoring the differentiation of melt viscosity in plate is to plate (plate-to-plate) flow graph at 260 DEG C.
Processed sample survey on after-vision by 30 minutes in stove at 250 DEG C and assess color stability.
Result is summed up in table 1 below.
| Character | Standard P A6.12 | Standard P A6.10 | The PA6.12 of preparation | The PA6.10 of preparation |
| Viscosity stability | +140% | +150% | +35% | +40% |
| Color stability | Brown | Brown | Yellow | Yellow |
table 1
These results prove, composition according to the present invention provides the stability better than standard composition.
embodiment 3 – Physical and mechanical properties of polyoropylene
Assess according to the fusing point of embodiment 1 or similar to Example 1 the four kinds of compositions prepared and straight resin flexible.
Fusing point is measured by differential scanning calorimetry (20 DEG C/min).
Straight resin flexibility is measured by mechanical test.
Result is summarised in following table 2.
| Character | Standard P A6.12 | Standard P A6.10 | The PA6.12 of preparation | The PA6.10 of preparation |
| Fusing point | 215℃ | 223℃ | 215℃ | 223℃ |
| Straight resin is flexible | 2100MPa | 2250MPa | 2100MPa | 2150MPa |
table 2
Result above proves relevant engineering properties hardly by the impact added of chain terminating agent.
Claims (12)
1. the monofilament prepared by daiamid composition, described daiamid composition comprises the polyamide obtained by the condensation of following material of at least 70 % by weight:
-comprise the aliphatic diamine of 4-18 carbon atom, and
-comprise aliphatic (alicyclic) diacid of 10-18 carbon atom, and
-as the aliphatic monocarboxylic acid comprising 2-12 carbon atom of chain terminating agent.
2. the monofilament of claim 1, wherein said aliphatic monocarboxylic acid is acetic acid and/or laurate.
3. the monofilament of claim 1 or 2, wherein said aliphatic diamine comprises 5-12 carbon atom, preferably 6 carbon atoms.
4. the monofilament of one of claim 1-3, wherein said polyamide is:
-there is the polyamide 6 .10 of acetamide-end group; Or
-there is the polyamide 6 .10 of lauramide-end group; Or
-there is the polyamide 6 .12 of acetamide-end group; Or
-there is the polyamide 6 .12 of lauramide-end group.
5. the monofilament of one of claim 1-4, wherein said daiamid composition comprises the described polyamide of at least 75 % by weight, preferably at least 80 % by weight or at least 85 % by weight or at least 90 % by weight or at least 95 % by weight or at least 98 % by weight or at least 99 % by weight.
6. the monofilament of one of claim 1-5, described daiamid composition also comprises one or more fluorescent whitening agents and/or one or more antioxidants except described polyamide, by one or more fluorescent whitening agents and/or one or more antioxidants, preferred described daiamid composition adds that described polyamide forms.
7. prepare the method for monofilament, comprise and daiamid composition is extruded through die head, wherein said daiamid composition comprises the polyamide obtained by the condensation of following material of at least 70 % by weight:
-comprise the aliphatic diamine of 4-18 carbon atom, and
-comprise aliphatic (alicyclic) diacid of 10-18 carbon atom, and
-as the aliphatic monocarboxylic acid comprising 2-12 carbon atom of chain terminating agent.
8. the method for claim 7, wherein said daiamid composition is as described in one of claim 1-6.
9. comprise the aliphatic monocarboxylic acid of 2-12 carbon atom as the purposes of chain terminating agent for the stable monofilament prepared by daiamid composition, described daiamid composition comprises the polyamide obtained by the condensation of following material of at least 70 % by weight:
-comprise the aliphatic diamine of 4-18 carbon atom, and
-comprise aliphatic (alicyclic) diacid of 10-18 carbon atom.
10. the purposes of claim 9, wherein said daiamid composition is as described in one of claim 1-6.
11. amenitiess comprising the monofilament of one of one or more claim 1-6, described amenities is preferably toothbrush.
12. cleaning supplies comprising the monofilament of one of one or more claim 1-6, described cleaning supplies are preferably brush.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310399020.6A CN104420001A (en) | 2013-09-04 | 2013-09-04 | Monofilament based on polyamide composition |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310399020.6A CN104420001A (en) | 2013-09-04 | 2013-09-04 | Monofilament based on polyamide composition |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB747614A (en) * | 1953-03-05 | 1956-04-11 | British Nylon Spinners Ltd | Improvements in the viscosity stabilisation of polyamides |
| GB948507A (en) * | 1961-05-23 | 1964-02-05 | British Nylon Spinners Ltd | Improvements in or relating to synthetic polymers |
| GB1042228A (en) * | 1964-09-24 | 1966-09-14 | British Nylon Spinners Ltd | Continuous production of polyamide articles |
| CN102558547A (en) * | 2012-02-20 | 2012-07-11 | 山东广垠新材料有限公司 | Preparation method for polyamide 1014 |
-
2013
- 2013-09-04 CN CN201310399020.6A patent/CN104420001A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB747614A (en) * | 1953-03-05 | 1956-04-11 | British Nylon Spinners Ltd | Improvements in the viscosity stabilisation of polyamides |
| GB948507A (en) * | 1961-05-23 | 1964-02-05 | British Nylon Spinners Ltd | Improvements in or relating to synthetic polymers |
| GB1042228A (en) * | 1964-09-24 | 1966-09-14 | British Nylon Spinners Ltd | Continuous production of polyamide articles |
| CN102558547A (en) * | 2012-02-20 | 2012-07-11 | 山东广垠新材料有限公司 | Preparation method for polyamide 1014 |
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Application publication date: 20150318 |
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